Search

The ground-state intermolecular dissociation energies D0(S0) of supersonic-jet cooled intermolecular complexes of 1-naphthol (1NpOH) with the bi- and tricycloalkanes trans-decalin, cis-decalin, and adamantane were measured using the stimulated-emission-pumping/resonant two-photon ionization (SEP-R2PI) method. Using UV/UV holeburning, we identified two isomers (A and B) of the adamantane and trans-decalin complexes and four isomers (A–D) of the cis-decalin complex. For 1NpOH·adamantane A and B, the D0(S0) values are 21.6 ± 0.15 kJ/mol and 21.2 ± 0.32 kJ/mol, those of 1NpOH·trans-decalin A and B are 28.7 ± 0.3 kJ/mol and 28.1 ± 0.9 kJ/mol, and those of 1NpOH·cis-decalin A and B are 28.9 ± 0.15 kJ/mol and 28.7 ± 0.3 kJ/mol. Upon S0 → S1 electronic excitation of the 1NpOH moiety, the dissociation energies of adamantane, trans-decalin, and the cis-decalin isomer C change by <1% and those of cis-decalin isomers A, B, and D increase only slightly (1%–3%). This implies that the hydrocarbons are dispersively adsorbed to a naphthalene "face." Calculations using the dispersion-corrected density functional theory methods B97-D3 and B3LYP-D3 indeed predict that the stable structures have face geometries. The B97-D3 calculated D0(S0) values are within 1 kJ/mol of the experiment, while B3LYP-D3 predicts D0 values that are 1.4–3.3 kJ/mol larger. Although adamantane has been recommended as a "dispersion-energy donor," the binding energies of the trans- and cis-decalin adducts to 1NpOH are 30% larger than that of adamantane. In fact, the D0 value of 1NpOH·adamantane is close to that of 1NpOH·cyclohexane, reflecting the nearly identical contact layer between the two molecules. [ABSTRACT FROM AUTHOR]

The S1 excited-state lifetime of jet-cooled 1-ethylcytosine (1ECyt) is ∼1 ns, one of the longest lifetimes for cytosine derivatives to date. Here, we analyze its S0 → S1 vibronic spectrum using two-color resonant two-photon ionization and UV/UV holeburning spectroscopy. Compared to cytosine and 1-methylcytosine, the S0 → S1 spectrum of 1ECyt shows a progression in the out-of-plane "butterfly" mode ν 1 ′ , identified by spin-component scaled-second-order coupled-cluster method ab initio calculations. We also report time-resolved S1 state nonradiative dynamics at ∼20 ps resolution by the pump/delayed ionization technique. The S1 lifetime increases with the number of ν 1 ′ quanta from τ = 930 ps at v 1 ′ = 0 to 1030 ps at v 1 ′ = 2 , decreasing to 14 ps at 710 cm−1 vibrational energy. We measured the rate constants for S1 ⇝ S0 internal conversion and S1 ⇝ T1 intersystem crossing (ISC): At the v′ = 0 level, kIC is 8 × 108 s−1 or three times smaller than 1-methylcytosine. The ISC rate constant from v′ = 0 to the T1(3ππ*) state is kISC = 2.4 × 108 s−1, 10 times smaller than the ISC rate constants of cytosine, but similar to that of 1-methylcytosine. Based on the calculated S1(1ππ*) state radiative lifetime τrad = 12 ns, the fluorescence quantum yield of 1ECyt is Φfl ∼ 7% and the intersystem crossing yield is ΦISC ∼ 20%. We measured the adiabatic ionization energy of 1-ethylcytosine via excitation of the S1 state as 8.353 ± 0.008 eV, which is 0.38 eV lower than that of amino-keto cytosine. Measurement of the ionization energy of the long-lived T1(ππ*) state formed via ISC reveals that it lies 3.2–3.4 eV above the S0 ground state. [ABSTRACT FROM AUTHOR]

The stimulated-emission-pumping/resonant 2-photon ionization (SEP-R2PI) method was used to determine the intermolecular dissociation energies D0 of jet-cooled 1-naphthol(1NpOH)·S complexes, where S is a linear molecule (N2, CO, CO2, OCS, N2O, and ethyne) or symmetric-top molecule (2-butyne) that contains double or triple bonds. The dissociation energies D0(S0) are bracketed as follows: 6.68 ± 0.08 kJ/mol for S=N2, 7.7 ± 0.8 kJ/mol for CO, 12.07 ± 0.10 kJ/mol for CO2, 13.03 ± 0.01 kJ/mol for N2O, 14.34 ± 0.08 kJ/mol for ethyne, 15.0 ± 1.35 kJ/mol for OCS, and 29.6 ± 2.4 kJ/mol for 2-butyne. The minimum-energy structures, vibrational wavenumbers, and zero-point vibrational energies were calculated using the dispersion-corrected density functional theory methods such as B97-D3 and B3LYP-D3 with the def2-QZVPP basis set. These predict that N2 and CO are dispersively bound Face complexes (S bound to a naphthalene Face), while CO2, N2O, and OCS adsorb into the "Notch" between the naphthyl and OH groups; these are denoted as Notch complexes. Ethyne and 2-butyne form Edge complexes involving H-bonds from the —OH group of 1NpOH to the center of the molecule. The presence of a double or triple bond or an aromatic C=C bond within S does not lead to a specific calculated geometry (Face, Notch or Edge). However, a correlation exists between the structure and the sign of the quadrupole moment component Θzz of S: negative Θzz correlates with Face or Notch, while positive Θzz correlates with Edge geometries. [ABSTRACT FROM AUTHOR]

We have measured the intermolecular dissociation energies D0 of supersonically cooled 1-naphthol (1NpOH) complexes with solvents S = furan, thiophene, 2,5-dimethylfuran, and tetrahydrofuran. The naphthol OH forms non-classical H-bonds with the aromatic π-electrons of furan, thiophene, and 2,5-dimethylfuran and a classical H-bond with the tetrahydrofuran O atom. Using the stimulated-emission pumping resonant two-photon ionization method, the ground-state D0(S0) values were bracketed as 21.8 ± 0.3 kJ/mol for furan, 26.6 ± 0.6 kJ/mol for thiophene, 36.5 ± 2.3 kJ/mol for 2,5-dimethylfuran, and 37.6 ± 1.3 kJ/mol for tetrahydrofuran. The dispersion-corrected density functional theory methods B97-D3, B3LYP-D3 (using the def2-TZVPP basis set), and ωB97X-D [using the 6-311++G(d,p) basis set] predict that the H-bonded (edge) isomers are more stable than the face isomers bound by dispersion; experimentally, we only observe edge isomers. We compare the calculated and experimental D0 values and extend the comparison to the previously measured 1NpOH complexes with cyclopropane, benzene, water, alcohols, and cyclic ethers. The dissociation energies of the nonclassically H-bonded complexes increase roughly linearly with the average polarizability of the solvent, α ¯ (S). By contrast, the D0 values of the classically H-bonded complexes are larger, increase more rapidly at low α ¯ (S), but saturate for large α ¯ (S). The calculated D0(S0) values for the cyclopropane, benzene, furan, and tetrahydrofuran complexes agree with experiment to within 1 kJ/mol and those of thiophene and 2,5-dimethylfuran are ∼3 kJ/mol smaller than experiment. The B3LYP-D3 calculated D0 values exhibit the lowest mean absolute deviation (MAD) relative to experiment (MAD = 1.7 kJ/mol), and the B97-D3 and ωB97X-D MADs are 2.2 and 2.6 kJ/mol, respectively. [ABSTRACT FROM AUTHOR]

Using the stimulated-emission-pumping/resonant 2-photon ionization (SEP-R2PI) method, we have determined accurate intermolecular dissociation energies D0 of supersonic jet-cooled intermolecular complexes of 1-naphthol (1NpOH) with alkanes, 1NpOH·S, with S = methane, ethane, propane, and n-butane. Experimentally, the smaller alkanes form a single minimum-energy structure, while 1-naphthol·n-butane forms three different isomers. The ground-state dissociation energies D0(S0) for the complexes with propane and n-butane (isomers A and B) were bracketed within ±0.5%, being 16.71 ± 0.08 kJ/mol for S = propane and 20.5 ± 0.1 kJ/mol for isomer A and 20.2 ± 0.1 kJ/mol for isomer B of n-butane. All 1NpOH·S complexes measured previously exhibit a clear dissociation threshold in their hot-band detected SEP-R2PI spectra, but weak SEP-R2PI bands are observed above the putative dissociation onset for the methane and ethane complexes. We attribute these bands to long-lived complexes that retain energy in rotation-type intermolecular vibrations, which couple only weakly to the dissociation coordinates. Accounting for this, we find dissociation energies of D0(S0) = 7.98 ± 0.55 kJ/mol (±7%) for S = methane and 14.5 ± 0.28 kJ/mol (±2%) for S = ethane. The D0 values increase by only 1% upon S0 → S1 excitation of 1-naphthol. The dispersion-corrected density functional theory methods B97-D3, B3LYP-D3, and ωB97X-D predict that the n-alkanes bind dispersively to the naphthalene “Face.” The assignment of the complexes to Face structures is supported by the small spectral shifts of the S0 → S1 electronic origins, which range from +0.5 to −15 cm−1. Agreement with the calculated dissociation energies D0(S0) is quite uneven, the B97-D3 values agree within 5% for propane and n-butane, but differ by up to 20% for methane and ethane. The ωB97X-D method shows good agreement for methane and ethane but overestimates the D0(S0) values for the larger n-alkanes by up to 20%. The agreement of the B3LYP-D3 D0 values is intermediate between the other two methods. [ABSTRACT FROM AUTHOR]

p-Dioxane is non-polar, hence its rotational constants cannot be determined by microwave rotational coherence spectroscopy (RCS). We perform high-resolution gas-phase rotational spectroscopy of para-dioxane-h8 and -d8 using femtosecond time-resolved Raman RCS in a gas cell at T = 293 K and in a pulsed supersonic jet at T ~ 130 K. The inertial tensor of p-dioxane-h8 is strongly asymmetric, leading to a large number of asymmetry transients in its RCS spectrum. In contrast, the d8-isotopomer is a near-oblate symmetric top that exhibits a much more regular RCS spectrum with few asymmetry transients. Fitting the fs Raman RCS transients of p-dioxane-h8 to an asymmetric-top model yields the ground-state rotational constants A0 = 5084.4(5) MHz, B0 = 4684(1) MHz, C0 = 2744.7(8) MHz, and (A0 + B0)/2 = 4884.5(7) MHz (±1σ±1σ). The analogous values for p-dioxane-d8 are A0 = 4083(2) MHz, B0 = 3925(4) MHz, C0 = 2347.1(6) MHz, and (A0 + B0)/2 = 4002.4(6) MHz. We determine the molecular structure with a semi-experimental approach involving the highly correlated coupled-cluster singles, doubles and iterated triples method and the cc-pCVXZ basis set series from double- to quadruple-zeta (X = D, T, Q). Combining the calculated vibrationally averaged rotational constants A0calC(X),B0calC(X),C0calC(X)A0calc(X),B0calc(X),C0calc(X) for increasing basis-set size X with non-linear extrapolation to the experimental constants Aexp0,Bexp0,Cexp0A0exp,B0exp,C0exp allows to determine the equilibrium ground state structure of p-dioxane. For instance, the equilibrium C-C and C-O bond lengths are re(CC) = 1.5135(3) Å and re(CO) = 1.4168(4) Å, and the four axial C-H bond lengths are 0.008 Å longer than the four equatorial ones. The latter is ascribed to the trans-effect (anomeric effect), i.e., the partial delocalization of the electron lone-pairs on the O atoms that are oriented trans, relative to the axial CH bonds. [ABSTRACT FROM AUTHOR]

We measure the S0→S1 spectrum and time-resolved S1 state nonradiative dynamics of the 'clamped' cytosine derivative 5,6-trimethylenecytosine (TMCyt) in a supersonic jet, using two-color resonant two-photon ionization (R2PI), UV/UV holeburning, and ns time-resolved pump/delayed ionization. The experiments are complemented with spin-component scaled second-order approximate coupled cluster (SCS-CC2), time-dependent density functional theory, and multi-state second-order perturbation-theory (MS-CASPT2) ab initio calculations. While the R2PI spectrum of cytosine breaks off ~500 cm1 above its 000 band, that of TMCyt extends up to +4400 cm-1 higher, with over a hundred resolved vibronic bands. Thus, clamping the cytosine C5-C6 bond allows us to explore the S1 state vibrations and S0→S1 geometry changes in detail. The TMCyt S1 state out-of-plane vibrations v'1, v'3, and v'5 lie below 420 cm-1, and the in-plane v'11, v'12, and v'23 vibrational fundamentals apper at 450, 470, and 944 cm-1. S0 → S1 vibronic simulations based on SCS-CC2 calculations agree well with experiment if the calculated v'1, v'3 , and v'5 frequencies are reduced by a factor of 2-3. MS-CASPT2 calculations predict that the ethylene-type S1 S0 conical intersection (CI) increases from +366 cm-1 in cytosine to >6000 cm-1 in TMCyt, explaining the long lifetime and extended S0→S1 spectrum. The lowest-energy S1 S0 CI of TMCyt is the "amino out-of-plane" (OPX) intersection, calculated at +4190 cm-1. The experimental S1 S0 internal conversion rate constant at the S1(v' = 0) level is kIC = 0.98-2.2 108 s-1, which is ~10 times smaller than in 1-methylcytosine and cytosine. The S1(v' = 0) level relaxes into the T1(3ππ*) state by intersystem crossing with kISC = 0.41-1.6 108 s-1. The T1 state energy is measured to lie 24 580 ± 560 cm-1 above the S0 state. The S1(v' = 0) lifetime is = 2.9 ns, resulting in an estimated fluorescence quantum yield of ϕfl = 24%. Intense two-color R2PI spectra of the TMCyt amino-enol tautomers appear above 36 000 cm-1. A sharp S1 ionization threshold is observed for amino-keto TMCyt, yielding an adiabatic ionization energy of 8.114 ± 0.002 eV. [ABSTRACT FROM AUTHOR]

The 1-naphthol·cyclopropane intermolecular complex is formed in a supersonic jet and investigated by resonant two-photon ionization (R2PI) spectroscopy, UV holeburning, and stimulated emission pumping (SEP)-R2PI spectroscopy. Two very different structure types are inferred from the vibronic spectra and calculations. In the "edge" isomer, the OH group of 1-naphthol is directed towards a C--C bond of cyclopropane, the two ring planes are perpendicular. In the "face" isomer, the cyclopropane is adsorbed on one of the π-aromatic faces of the 1-naphthol moiety, the ring planes are nearly parallel. Accurate ground-state intermolecular dissociation energies D0 were measured with the SEP-R2PI technique. The D0(S0) of the edge isomer is bracketed as 15.35 « 0.03 kJ/mol, while that of the face isomer is 16.96 « 0.12 kJ/mol. The corresponding excited-state dissociation energies D0(S1) were evaluated using the respective electronic spectral shifts. Despite the D0(S0) difference of 1.6 kJ/mol, both isomers are observed in the jet in similar concentrations, so they must be separated by substantial potential energy barriers. Intermolecular binding energies, De, and dissociation energies, D0, calculated with correlated wave function methods and two dispersion-corrected density-functional methods are evaluated in the context of these results. The density functional calculations suggest that the face isomer is bound solely by dispersion interactions. Binding of the edge isomer is also dominated by dispersion, which makes up two thirds of the total binding energy. [ABSTRACT FROM AUTHOR]

We have investigated the S0 → S1 UV vibronic spectrum and time-resolved S1 state dynamics of jet-cooled amino-keto 1-methylcytosine (1MCyt) using two-color resonant two-photon ionization, UV/UV holeburning and depletion spectroscopies, as well as nanosecond and picosecond timeresolved pump/delayed ionization measurements. The experimental study is complemented with spin-component-scaled second-order coupled-cluster and multistate complete active space second order perturbation ab initio calculations. Above the weak electronic origin of 1MCyt at 31 852 cm-1 about 20 intense vibronic bands are observed. These are interpreted as methyl group torsional transitions coupled to out-of-plane ring vibrations, in agreement with the methyl group rotation and out-of-plane distortions upon 1ππ* excitation predicted by the calculations. The methyl torsion and ν′1 (butterfly) vibrations are strongly coupled, in the S1 state. The S0 → S1 vibronic spectrum breaks off at a vibrational excess energy Eexc ~ 500 cm-1, indicating that a barrier in front of the ethylene-type S1 S0 conical intersection is exceeded, which is calculated to lie at Eexc = 366 cm-1. The S1 ⇝ S0 internal conversion rate constant increases from kIC = 2 · 109 s-1 near the S1(ν = 0) level to 1 · 1011 s-1 at Eexc = 516 cm-1. The 1ππ* state of 1MCyt also relaxes into the lower-lying triplet T1 (3ππ*) state by intersystem crossing (ISC); the calculated spin-orbit coupling (SOC) value is 2.4 cm-1. The ISC rate constant is 10-100 times lower than kIC; it increases from kISC = 2 · 108 s-1 near S1(ν = 0) to kISC = 2 · 109 s-1 at Eexc = 516 cm-1. The T1 state energy is determined from the onset of the time-delayed photoionization efficiency curve as 25 600 ± 500 cm-1. The T2 (3nπ*) state lies >1500 cm-1 above S1(ν = 0), so S1 ⇝ T2 ISC cannot occur, despite the large SOC parameter of 10.6 cm-1. An upper limit to the adiabatic ionization energy of 1MCyt is determined as 8.41 ± 0.02 eV. Compared to cytosine, methyl substitution at N1 lowers the adiabatic ionization energy by ≥0.32 eV and leads to a much higher density of vibronic bands in the S0 → S1 spectrum. The effect of methylation on the radiationless decay to S0 and ISC to T1 is small, as shown by the similar break-off of the spectrum and the similar computed mechanisms. [ABSTRACT FROM AUTHOR]

The amino-keto tautomer of supersonic jet-cooled cytosine undergoes intersystem crossing (ISC) from the v = 0 and low-lying vibronic levels of its S1(¹ππ*) state. We investigate these ISC rates experimentally and theoretically as a function of S1 state vibrational excess energy Eexc. The S1 vibronic levels are pumped with a ~5 ns UV laser, the S1 and triplet state ion signals are separated by prompt or delayed ionization with a second UV laser pulse. After correcting the raw ISC yields for the relative S1 and T1 ionization cross sections, we obtain energy dependent ISC quantum yields QISCcorr=1%-5%. These are combined with previously measured vibronic state-specific decay rates, giving ISC rates kISC = 0.4-1.5 · 109 s-1, the corresponding S1 ⇝S0 internal conversion (IC) rates are 30-100 times larger. Theoretical ISC rates are computed using SCS-CC2 methods, which predict rapid ISC from the S1; v = 0 state with kISC = 3. 109 s-1 to the T1(3ππ*) triplet state. The surprisingly high rate of this El Sayed-forbidden transition is caused by a substantial admixture of ¹nOπ* character into the S1(¹ππ*) wave function at its non-planar minimum geometry. The combination of experiment and theory implies that (1) below Eexc = 550 cm-1 in the S1 state, S1 ⇝S0 internal conversion dominates the nonradiative decay with kIC ≥ 2 . 1010 s-1, (2) the calculated S1⇝T1 (¹π#960;*³ππ*) ISC rate is in good agreement with experiment, (3) being El-Sayed forbidden, the S1 ⇝ T1 ISC is moderately fast (kISC = 3. 109 s-1), and not ultrafast, as claimed by other calculations, and (4) at Eexc ~ 550 cm-1 the IC rate increases by ~50 times, probably by accessing the lowest conical intersection (the C5-twist CI) and thereby effectively switching off the ISC decay channels. [ABSTRACT FROM AUTHOR]

Femtosecond Raman rotational coherence spectroscopy (RCS) detected by degenerate four-wave mixing is a background-free method that allows to determine accurate gas-phase rotational constants of non-polar molecules. Raman RCS has so far mostly been applied to the regular coherence patterns of symmetric-top molecules, while its application to nonpolar asymmetric tops has been hampered by the large number of RCS transient types, the resulting variability of the RCS patterns, and the 103–104 times larger computational effort to simulate and fit rotational Raman RCS transients. We present the rotational Raman RCS spectra of the nonpolar asymmetric top 1,4-difluorobenzene (para-difluorobenzene, p-DFB) measured in a pulsed Ar supersonic jet and in a gas cell over delay times up to ∼2.5 ns. p-DFB exhibits rotational Raman transitions with ΔJ = 0, 1, 2 and ΔK = 0, 2, leading to the observation of J −, K −, A −, and C–type transients, as well as a novel transient (S–type) that has not been characterized so far. The jet and gas cell RCS measurements were fully analyzed and yield the ground-state (v = 0) rotational constants A0 = 5637.68(20) MHz, B0 = 1428.23(37) MHz, and C0 = 1138.90(48) MHz (1σ uncertainties). Combining the A0, B0, and C0 constants with coupled-cluster with single-, double- and perturbatively corrected triple-excitation calculations using large basis sets allows to determine the semi-experimental equilibrium bond lengths re(C1–C2) = 1.3849(4) Å, re(C2–C3) = 1.3917(4) Å, re(C–F) = 1.3422(3) Å, and re(C2–H2) = 1.0791(5) Å. [ABSTRACT FROM AUTHOR]

We observe the weak S0 → S2 transitions of the T-shaped benzene dimers (Bz)2 and (Bz-d6)2 about 250 cm−1 and 220 cm−1 above their respective S0 → S 1 electronic origins using two-color resonant two-photon ionization spectroscopy. Spin-component scaled (SCS) second-order approximate coupled-cluster (CC2) calculations predict that for the tipped T-shaped geometry, the S0 → S2 electronic oscillator strength fel(S2) is ~10 times smaller than fel(S1) and the S2 state lies ~240 cm−1 above S1, in excellent agreement with experiment. The S0 → S1 (ππ *) transition is mainly localized on the “stem” benzene, with a minor stem → cap charge-transfer contribution; the S0 → S2 transition is mainly localized on the “cap” benzene. The orbitals, electronic oscillator strengths fel(S1) and fel(S2), and transition frequencies depend strongly on the tipping angle ω between the two Bz moieties. The SCS-CC2 calculated S1 and S2 excitation energies at different T-shaped, stacked-parallel and parallel-displaced stationary points of the (Bz)2 ground-state surface allow to construct approximate S1 and S2 potential energy surfaces and reveal their relation to the “excimer” states at the stacked-parallel geometry. The fel(S1) and fel(S2) transition dipole moments at the C2v -symmetric T-shape, parallel-displaced and stacked-parallel geometries are either zero or ~10 times smaller than at the tipped T-shaped geometry. This unusual property of the S0 → S1 and S0 → S2 transition-dipole moment surfaces of (Bz)2 restricts its observation by electronic spectroscopy to the tipped and tilted T-shaped geometries; the other ground-state geometries are impossible or extremely difficult to observe. The S0 → S1/S2 spectra of (Bz)2 are compared to those of imidazole ⋅ (Bz)2, which has a rigid triangular structure with a tilted (Bz)2 subunit. The S0 → S1/ S2 transitions of imidazole-(benzene)2 lie at similar energies as those of (Bz)2, confirming our assignment of the (Bz)2 S0 → S2 transition. [ABSTRACT FROM AUTHOR]

The S2 ↏ S1 vibronic spectrum of the ortho-cyanophenol dimer (oCP)2 is analyzed in a joint experimental and theoretical investigation. Vibronic excitation energies up to 750 cm-1 are covered, which extends our previous analysis of the quenching of the excitonic splitting in this and related species [Kopec et al., J. Chem. Phys. 137, 184312 (2012)]. As we demonstrate, this necessitates an extension of the coupling model. Accordingly, we compute the potential energy surfaces of the orthocyanophenol dimer (oCP)2 along all relevant normal modes using the approximate second-order coupled cluster method RI-CC2 and extract the corresponding coupling constants using the linear and quadratic vibronic coupling scheme. These serve as the basis to calculate the vibronic spectrum. The theoretical results are found to be in good agreement with the experimental highly resolved resonant two-photon ionization spectrum. This allows to interpret key features of the excitonic and vibronic interactions in terms of nodal patterns of the underlying vibronic wave functions. [ABSTRACT FROM AUTHOR]

The gas-phase rotational motion of hexafluorobenzene has been measured in real time using femtosecond (fs) time-resolved rotational Raman coherence spectroscopy (RR-RCS) at T = 100 and 295 K. This four-wave mixing method allows to probe the rotation of non-polar gasphase molecules with fs time resolution over times up to ~5 ns. The ground state rotational constant of hexafluorobenzene is determined as B0 = 1029.740(28) MHz (2σ uncertainty) from RR-RCS transients measured in a pulsed seeded supersonic jet, where essentially only the v = 0 state is populated. Using this B0 value, RR-RCS measurements in a room temperature gas cell give the rotational constants Bv of the five lowest-lying thermally populated vibrationally excited states v7/8, v9, v11/12, v13, and v14/15. Their Bv constants differ from B0 by between -1.02 MHz and +2.23 MHz. Combining the B0 with the results of all-electron coupled-cluster CCSD(T) calculations of Demaison et al. [Mol. Phys. 111, 1539 (2013)] and of our own allow to determine the C-C and C-F semi-experimental equilibrium bond lengths re(C-C) = 1.3866(3) Å and re(C-F) = 1.3244(4) Å. These agree with the CCSD(T)/wCVQZ re bond lengths calculated by Demaison et al. within ±0.0005 Å. We also calculate the semi-experimental thermally averaged bond lengths rg(C-C)=1.3907(3) Å and rg(C-F)=1.3250(4) Å. These are at least ten times more accurate than two sets of experimental gas-phase electron diffraction rg bond lengths measured in the 1960s. [ABSTRACT FROM AUTHOR]

The UV spectrum of the adenine analogue 9-methyl-2-aminopurine (9M-2AP) is investigated with one- and two-color resonant two-photon ionization spectroscopy at 0.3 and 0.05 cm-1 resolution in a supersonic jet. The electronic origin at 32 252 cm-1 exhibits methyl torsional subbands that originate from the 0A1″ (l = 0) and 1E″ (l = ±1) torsional levels. These and further torsional bands that appear up to 000+ 230 cm-1 allow to fit the threefold (V3) barriers of the torsional potentials as ∣V3′∣ = 50 cm-1 in the S0 and ∣V3′∣ = 126 cm-1 in the S1 state. Using the B3LYP density functional and correlated approximate second-order coupled cluster CC2 methods, the methyl orientation is calculated to be symmetric relative to the 2AP plane in both states, with barriers of V3″= 20 cm-1 and V3′ = 115 cm-1. The 000rotational band contour is 75% in-plane (a/b) polarized, characteristic for a dominantly long-axis ¹ππ* excitation. The residual 25% c-axis polarization may indicate coupling of the ¹ππ* to the close-lying ¹nπ* state, calculated at 4.00 and 4.01 eV with the CC2 method. However, the CC2 calculated ¹nπ oscillator strength is only 6% of that of the ¹ππ* transition. The ¹ππ* vibronic spectrum is very complex, showing about 40 bands within the lowest 500 cm-1. The methyl torsion and the low-frequency out-of-plane ν1′ and ν2′ vibrations are strongly coupled in the ¹ππ* state. This gives rise to many torsion-vibration combination bands built on out-of-plane fundamentals, which are without precedence in the ¹ππ* spectrum of 9H-2-aminopurine [S. Lobsiger, R. K. Sinha, M. Trachsel, and S. Leutwyler, J. Chem. Phys. 134, 114307 (2011)]. From the Lorentzian broadening needed to fit the 000 contour of 9M-2AP, the ¹ππ* lifetime is τ ≥ 120 ps, reflecting a rapid nonradiative transition. [ABSTRACT FROM AUTHOR]

The benzoic acid dimer, (BZA)2, is a paradigmatic symmetric hydrogen bonded dimer with two strong antiparallel hydrogen bonds. The excitonic S1/S2 state splitting and coherent electronic energy transfer within supersonically cooled (BZA)2 and its 13C-, d1 -, d2 -, and 13C/d1 - isotopomers have been investigated by mass-resolved two-color resonant two-photon ionization spectroscopy. The (BZA)2-(h - h) and (BZA)2-(d - d) dimers are C2h symmetric, hence only the S2 ← S0 transition can be observed, the S1 ← S0 transition being strictly electric-dipole forbidden. A single 12C/13C or H/D isotopic substitution reduces the symmetry of the dimer to Cs, so that the isotopic heterodimers (BZA)2 - 13C, (BZA)2 -(h - d), (BZA)2 -(h13C-d), and (BZA)2 -(h - d13C) show both S1 ← S0 and S2 ← S0 bands. The S1/S2 exciton splitting inferred is Δexc = 0.94 ± 0.1 cm-1. This is the smallest splitting observed so far for any H-bonded gas-phase dimer. Additional isotope-dependent contributions to the splittings, Δiso, arise from the change of the zero-point vibrational energy upon electronic excitation and range from Δiso = 3.3 cm-1 upon 12C/13C substitution to 14.8 cm-1 for carboxy H/D substitution. The degree of excitonic localization/delocalization can be sensitively measured via the relative intensities of the S1 ← S0 and S2 ← S0 origin bands; near-complete localization is observed even for a single 12C/13C substitution. The S1/ S2 energy gap of (BZA)2 is Δcalcexc=11 cm-1 when calculated by the approximate second-order perturbation theory (CC2) method. Upon correction for vibronic quenching, this decreases to Δvibronexc=2.1 cm-1 [P. Ottiger et al., J. Chem. Phys. 136, 174308 (2012)], in good agreement with the observed Δexc = 0.94 cm-1. The observed excitonic splittings can be converted to exciton hopping times τexc. For the (BZA)2-(h - h) homodimer τexc = 18 ps, which is nearly 40 times shorter than the double proton transfer time of (BZA)2 in its excited state [Kalkman et al., ChemPhysChem 9, 1788 (2008)]. Thus, the electronic energy transfer is much faster than the proton-transfer in (BZA)2*. [ABSTRACT FROM AUTHOR]

The quenching of the excitonic splitting in hydrogen-bonded molecular dimers has been explained recently in terms of exciton coupling theory, involving Förster's degenerate perturbation theoretical approach [P. Ottiger, S. Leutwyler, and H. Köppel, J. Chem. Phys. 136, 174308 (2012)]. Here we provide an alternative explanation based on the properties of the adiabatic potential energy surfaces. In the proper limit, the lower of these surfaces exhibits a double-minimum shape, with an asymmetric distortion that destroys the geometric equivalence of the excitonically coupled monomers. An effective mode is introduced that exactly reproduces the energy gain and amount of distortion that occurs in a multi-dimensional normal coordinate space. This allows to describe the quenched exciton splitting as the energy difference of the two (S1 and S2) vibronic band origins in a one-dimensional (rather than multi-dimensional) vibronic calculation. The agreement with the earlier result (based on Förster theory) is excellent for all five relevant cases studied. A simple rationale for the quenched exciton splitting as nonadiabatic tunneling splitting on the lower double-minimum potential energy surface is given. [ABSTRACT FROM AUTHOR]

The excitonic splitting between the S1 and S2 electronic states of the doubly hydrogen-bonded dimer 2-pyridone·6-methyl-2-pyridone (2PY·6M2PY) is studied in a supersonic jet, applying two-color resonant two-photon ionization (2C-R2PI), UV-UV depletion, and dispersed fluorescence spectroscopies. In contrast to the C2h symmetric (2-pyridone)2 homodimer, in which the S1 ← S0 transition is symmetry-forbidden but the S2 ← S0 transition is allowed, the symmetry-breaking by the additional methyl group in 2PY·6M2PY leads to the appearance of both the S1 and S2 origins, which are separated by Δexp = 154 cm-1. When combined with the separation of the S1 ← S0 excitations of 6M2PY and 2PY, which is δ = 102 cm-1, one obtains an S1/S2 exciton coupling matrix element of VAB, el = 57 cm-1 in a Frenkel-Davydov exciton model. The vibronic couplings in the S1/S2 ← S0 spectrum of 2PY·6M2PY are treated by the Fulton-Gouterman single-mode model. We consider independent couplings to the intramolecular 6a′ vibration and to the intermolecular σ′ stretch, and obtain a semi-quantitative fit to the observed spectrum. The dimensionless excitonic couplings are C(6a′) = 0.15 and C(σ′) = 0.05, which places this dimer in the weak-coupling limit. However, the S1/S2 state exciton splittings Δcalc calculated by the configuration interaction singles method (CIS), time-dependent Hartree-Fock (TD-HF), and approximate second-order coupled-cluster method (CC2) are between 1100 and 1450 cm-1, or seven to nine times larger than observed. These huge errors result from the neglect of the coupling to the optically active intra- and intermolecular vibrations of the dimer, which lead to vibronic quenching of the purely electronic excitonic splitting. For 2PY·6M2PY the electronic splitting is quenched by a factor of ∼30 (i.e., the vibronic quenching factor is Γexp = 0.035), which brings the calculated splittings into close agreement with the experimentally observed value. The 2C-R2PI and fluorescence spectra of the tautomeric species 2-hydroxypyridine·6-methyl-2-pyridone (2HP·6M2PY) are also observed and assigned. [ABSTRACT FROM AUTHOR]

We have investigated the UV vibronic spectra and excited-state nonradiative processes of the 7H- and 9H-tautomers of jet-cooled 2-aminopurine (2AP) and of the 9H-2AP-d4 and -d5 isotopomers, using two-color resonant two-photon ionization spectroscopy at 0.3 and 0.045 cm-1 resolution. The S1 ← S0 transition of 7H-2AP was observed for the first time. It lies ∼ 1600 cm-1 below that of 9H-2AP, is ∼1000 times weaker and exhibits only in-plane vibronic excitations. In contrast, the S1 ← S0 spectra of 9H-2AP, 9H-2AP-d4, and 9H-2AP-d5 show numerous low-frequency bands that can be systematically assigned to overtone and combinations of the out-of-plane vibrations ν1′, ν2′, and ν3′. The intensity of these out-of-plane bands reflects an out-of-plane deformation in the 1ππ*(La) state. Approximate second-order coupled-cluster theory also predicts that 2-aminopurine undergoes a 'butterfly' deformation in its lowest 1ππ* state. The rotational contours of the 9H-2AP, 9H-2AP-d4, and 9H-2AP-d5 000 bands and of eight vibronic bands of 9H-2AP up to 000+600 cm-1 exhibit 75%-80% in-plane (a/b) polarization, which is characteristic for a 1ππ* excitation. A 20%-25% c-axis (perpendicular) transition dipole moment component may indicate coupling of the 1ππ* bright state to the close-lying 1nπ* dark state. However, no 1nπ* vibronic bands were detected below or up to 500 cm-1 above the 1ππ* 000 band. Following 1ππ* excitation, 9H-2AP undergoes a rapid nonradiative transition to a lower-lying long-lived state with a lifetime >=5μs. The ionization potential of 9H-2AP was measured via the 1ππ* state (IP = 8.020 eV) and the long-lived state (IP > 9.10 eV). The difference shows that the long-lived state lies >=1.08 eV below the 1ππ* state. Time-dependent B3LYP calculations predict the 3ππ* (T1) state 1.12 eV below the 1ππ* state, but place the 1nπ* (S1) state close to the 1ππ* state, implying that the long-lived state is the lowest triplet (T1) and not the 1nπ* state. [ABSTRACT FROM AUTHOR]

We analyze the vibronic band structure of the excitonically coupled S1←S0/S2←S0 excitations of the 2-aminopyridine (2AP) self-dimer (2AP)2, using a linear vibronic coupling model [R. Fulton and M. Gouterman, J. Chem. Phys. 41, 2280 (1964)]. The vibronic spectra of supersonically cooled (2AP)2 and its 13C-isotopomer were measured by two-color resonant two-photon ionization and UV/UV-depletion spectroscopies. In the C2-symmetric form of (2AP)2, the S1←S0 (1A←1A) transition is very weak, while the close-lying S2←S0 (1B←1A) transition is fully allowed. A single 12C/13C isotopic substitution breaks the symmetry of the dimer so that the (2AP)2-13C isotopologue exhibits both S1 and S2 electronic origins, which are split by 11 cm-1. In Fulton–Gouterman-type treatments, the linear vibronic coupling is mediated by intramolecular vibrational modes and couplings to intermolecular vibrations are not considered. For (2AP)2, a major vibronic coupling contribution arises from the intramolecular 6a′ vibration. However, the low-energy part of the spectrum is dominated by intermolecular shear (χ′) and stretching (σ′) vibrational excitations that also exhibit excitonic splittings; we apply a linear vibronic coupling analysis for these also. The respective excitation transfer integrals VAB are 50%–80% of that of the intramolecular 6a′ vibration, highlighting the role of intermolecular vibrations in mediating electronic energy exchange. The S1/S2 electronic energy gap calculated by the approximate second-order coupled-cluster method is ∼340 cm-1. This purely electronic exciton splitting is quenched by a factor of 40 by the vibronic couplings to the Franck–Condon active intramolecular vibrations. [ABSTRACT FROM AUTHOR]

We report electronic absorption spectra, recorded using one- and two-color resonance-enhanced multiphoton ionization spectroscopy, of the Au–Kr complex. The transition is localized on the gold atom, and corresponds to a 6p←6s atomic excitation; we observe transitions to the D 2Π1/2 and D 2Π3/2 spin-orbit states. In addition, we report the results of ab initio calculations, which consider electronic states arising from the 6 2S, 5 2D, and 6 2P atomic energy levels of Au. Further, we also report an accurate value for the dissociation energy of the ground state of Au–Kr, based on basis set extrapolated RCCSD(T) calculations. The experimental results are discussed in the light of the theoretical ones. [ABSTRACT FROM AUTHOR]

Spectral tuning effects on visible chromophores by hydrogen bonds are central to the chemistry of vision and of photosynthesis. A model for large spectral tuning effects by hydrogen bond switching is provided by the 7-hydroxyquinoline·HCOOH complex, which forms two isomers, CTN1 and CTN2, both with an HCOOH...N hydrogen bond but with different (quinoline)C–H...O==C hydrogen bonds. A 180° rotation of the HCOOH moiety around the O–H...N hydrogen bond exchanges the C–H...O hydrogen bonds, rotates the dipole moment of HCOOH, and leads to an ∼850 cm-1 shift of the electronic spectrum. Mass-selected S1←S0 resonant two-photon ionization, UV-UV holeburning, S1→S0 fluorescence spectra, and photoionization efficiency curves of the two 7-hydroxyquinoline·HCOOH isomers were measured in supersonic expansions. Comparison to ab initio calculations allow us to determine the H-bond connectivity and structure of the two isomers and to assign their inter- and intramolecular vibrations. The Franck-Condon factors of the intermolecular shear vibration χ in the S1←S0 spectra indicate that the weak C–H...O hydrogen bond contracts markedly in the CTN1 isomer but expands in the CTN2 isomer. These changes of H-bond lengths agree with the spectral shifts. In contrast, the strong O–H...N hydrogen bond undergoes little change upon S1←S0 excitation. [ABSTRACT FROM AUTHOR]

The S1↔S0 vibronic spectra of supersonic jet-cooled 2-pyridone [pyridin-2-one (2PY)] and its N–H deuterated isotopomer (d-2PY) have been recorded by two-color resonant two-photon ionization, laser-induced fluorescence and emission, and fluorescence depletion spectroscopies. By combining these methods, the B origin of 2PY at 000+98 cm-1 and the bands at +218 and +252 cm-1 are identified as overtones of the S1 state out-of-plane vibrations ν1′ and ν2′, as are the analogous bands of d-2PY. Anharmonic double-minimum potentials are derived for the respective out-of-plane coordinates that predict further ν1′ and ν2′ overtones and combinations, reproducing ∼80% of the vibronic bands up to 600 cm-1 above the 000 band. The fluorescence spectra excited at the electronic origins and the ν1′ and ν2′ out-of-plane overtone levels confirm these assignments. The S1 nonplanar minima and S1←S0 out-of-plane progressions are in agreement with the determination of nonplanar vibrationally averaged geometries for the 000 and 000+98 cm-1 upper states by Held et al. [J. Chem. Phys. 95, 8732 (1991)]. The fluorescence lifetimes of the S1 state vibrations show strong mode dependence: Those of the out-of-plane levels decrease rapidly above 200 cm-1 excess vibrational energy, while the in-plane vibrations ν5′, ν8′, and ν9′ have longer lifetimes, although they are above or interspersed with the “dark” out-of-plane states. This is interpreted in terms of an S1′ state reaction with a low barrier towards a conical intersection with a prefulvenic geometry. Out-of-plane vibrational states can directly surmount this barrier, whereas in-plane vibrations are much less efficient in this respect. Analysis of the fluorescence spectra allows to identify nine in-plane S0′ state fundamentals, overtones of the S0 state ν1″ and ν2″ out-of-plane vibrations, and >30 other overtones and combination bands. The B3LYP/6-311++G(d,p) calculated anharmonic wave numbers are in very good agreement with the observed fundamentals, overtones, and combinations, with a deviation Δrms=1.3%. [ABSTRACT FROM AUTHOR]

Femtosecond degenerate four-wave mixing (fs-DFWM) rotational coherence spectroscopy (RCS) has been used to determine the rotational and centrifugal distortion constants of the 00 00 ground and 01 10 vibrationally excited states of gas-phase CS2. RCS transients were recorded over the 0–3300 ps optical delay range, allowing the observation of 87 recurrences. The fits yield rotational constants B00 00=3.271 549 2(18) GHz for 12C32S2 and B00 00=3.175 06(21) GHz for the 12C32S34S isotopomer. The rotational constants of the degenerate 01 10 bending level of 12C32S2 are B01 10=3.276 72(40) and 3.279 03(40) GHz for the e and f substrates, respectively. These fs-DFWM rotational constants are ten times more accurate than those obtained by CO2 laser/microwave heterodyne measurements and are comparable to those obtained by high-resolution Fourier transform infrared spectroscopy. Ab initio calculations were performed at two levels, second-order Mo\ller-Plesset theory and coupled-cluster singles, doubles, and iterative triples [CCSD(T)]. The equilibrium and vibrationally averaged C==S distances were calculated using large Dunning basis sets. An extrapolation procedure combining the ab initio rotational constants with the experiment yields an equilibrium C==S bond length of 155.448 pm to an accuracy of ±20 fm. The theoretical C==S bond length obtained by a complete basis set extrapolation at the CCSD(T) level is re(C==S)=155.579 pm, or 0.13 pm longer than that in the experiment. [ABSTRACT FROM AUTHOR]

Femtosecond degenerate four-wave mixing (fs-DFWM) is applied for the measurement of rotational constants of cyclopropane (C3H6). The rotational coherence method yields a very accurate B0=20 093.322(12) MHz and centrifugal distortion constants DJ and DJK. To exploit the full resolution of the fs-DFWM method, the accuracy of the optical delay measurement was increased by nearly two orders of magnitude, including elimination of effects from the refractive index of air. The fs-DFWM molecular constants are comparable in accuracy to those from high-resolution infrared spectroscopy and are only surpassed by those of dipole distortion microwave spectroscopy. In parallel, the equilibrium structure, vibrationally averaged structure parameters and rotational constants were calculated using high-level ab initio methods and large basis sets. Combining these with the results of previous calculations and the measured rotational constants yields re(C–C)=1.5034(3) Å, re(C–H)=1.0775(5) Å, and αe(H–C–H)=115.09(10)°. [ABSTRACT FROM AUTHOR]

The excited-state hydrogen-atom transfer (ESHAT) reaction of the 7-hydroxyquinoline·(NH3)3 cluster involves a crossing from the initially excited 1ππ* to a 1πσ* state. The nonadiabatic coupling between these states induces homolytic dissociation of the O–H bond and H-atom transfer to the closest NH3 molecule, forming a biradical structure denoted HT1, followed by two more Grotthus-type translocation steps along the ammonia wire. We investigate this reaction at the configuration interaction singles level, using a basis set with diffuse orbitals. Intrinsic reaction coordinate calculations of the enol→HT1 step predict that the H-atom transfer is preceded and followed by extensive twisting and bending of the ammonia wire, as well as large O–H...NH3 hydrogen bond contraction and expansion. The calculations also predict an excited-state proton transfer path involving synchronous proton motions; however, it lies 20–25 kcal/mol above the ESHAT path. Higher singlet and triplet potential curves are calculated along the ESHAT reaction coordinate: Two singlet-triplet curve crossings occur within the HT1 product well and intersystem crossing to these Tn states branches the reaction back to the enol reactant side, decreasing the ESHAT yield. In fact, a product yield of ≈40% 7-ketoquinoline·(NH3)3 is experimentally observed. The vibrational mode selectivity of the enol→HT1 reaction step [C. Manca, C. Tanner, S. Coussan, A. Bach, and S. Leutwyler, J. Chem. Phys. 121, 2578 (2004)] is shown to be due to the large sensitivity of the diffuse πσ* state to vibrational displacements along the intermolecular coordinates. [ABSTRACT FROM AUTHOR]

The 2-aminopyridine·2-pyridone (2AP·2PY) dimer is linked by N–H...O==C and N–H...N hydrogen bonds, providing a model for the Watson–Crick hydrogen bond configuration of the adenine·thymine and adenine·uracil nucleobase pairs. Mass-specific infrared spectra of 2AP·2PY and its seven N–H deuterated isotopomers have been measured between 2550 and 3650 cm-1 by IR laser depletion combined with UV two-color resonant two-photon ionization. The 2PY amide N–H stretch is a very intense band spread over the range 2700–3000 cm-1 due to large anharmonic couplings. It is shifted to lower frequency by 710 cm-1 or ≈20% upon H bonding to 2AP. On the 2AP moiety, the “bound” amino N–H stretch gives rise to a sharp band at 3140 cm-1, which is downshifted by 354 cm-1 or ≈10% upon H bonding to 2PY. The amino group “free” N–H stretch and the H–N–H bend overtone are sharp bands at ≈3530 cm-1 and 3320 cm-1. Ab initio structures and harmonic vibrations were calculated at the Hartree–Fock level and with the PW91 and B3LYP density functionals. The PW91/6-311++G(d,p) method provides excellent predictions for the frequencies and IR intensities of all the isotopomers.© 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Excitation of the 7-hydroxyquinoline·(NH3)3 [7HQ·(NH3)3] cluster to the S1 1ππ* state results in an O-H→NH3 hydrogen atom transfer (HAT) reaction. In order to investigate the entrance channel, the vibronic S1↔S0 spectra of the 7HQ·(NH3)3 and the d2-7DQ·(ND3)3 clusters have been studied by resonant two-photon ionization, UV-UV depletion and fluorescence techniques, and by ab initio calculations for the ground and excited states. For both isotopomers, the low-frequency part of the S1←S0 spectra is dominated by ammonia-wire deformation and stretching vibrations. Excitation of overtones or combinations of these modes above a threshold of 200–250 cm-1 for 7HQ·(NH3)3 accelerates the HAT reaction by an order of magnitude or more. The d2-7DQ·(ND3)3 cluster exhibits a more gradual threshold from 300 to 650 cm-1. For both isotopomers, intermolecular vibrational states above the threshold exhibit faster HAT rates than the intramolecular vibrations. The reactivity, isotope effects, and mode selectivity are interpreted in terms of H atom tunneling through a barrier along the O-H→NH3 coordinate. The barrier results from a conical intersection of the optically excited 1ππ* state with an optically dark 1πσ* state. Excitation of the ammonia-wire stretching modes decreases both the quinoline-O-H...NH3 distance and the energetic separation between the 1ππ* and 1πσ* states, thereby increasing the H atom tunneling rate. The intramolecular vibrations change the H bond distance and modulate the 1ππ*↔1 interaction to a much smaller extent. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]* interaction to a much smaller extent. © 2004 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Mass-selected S[sub 1]↔S[sub 0] two color resonant two photon ionization (2C-R2PI) spectra, fluorescence spectra and fluorescence decay times are measured for supersonically cooled 7-hydroxyquinoline (7HQ)·(NH[sub 3])[sub n] clusters with n=4–10. For n=4, the S[sub 1]←S[sub 0] 2C-R2PI spectrum shows a 20 cm[sup -1] broad electronic origin at 27 746 cm[sup -1], followed by an intermolecular vibrational progression with band widths that increase up to ≈45 cm[sup -1]. In contrast, the 2C-R2PI spectra of the mixed 7HQ·(NH[sub 3])[sub 3]H[sub 2]O and 7HQ·(NH[sub 3])[sub 2](H[sub 2]O)[sub 2] clusters exhibit narrow bands of 1–2 cm[sup -1] width. The large band widths of 7HQ·(NH[sub 3])[sub 4] are due to a fast (k>10[sup 12] s[sup -1]) excited state process which is blocked when replacing one or more NH[sub 3] molecules by H[sub 2]O in the cluster. For the n=5–10 clusters, the 2C-R2PI spectra display two broad absorption bands peaking at 25 000 and 27 000 cm[sup -1]. The latter is characteristic of the 7-quinolinate (7Q[sup -]) anion, implying that ground state proton transfer from 7HQ to the ammonia cluster occurs for n>=5. Excitation at 27 000 cm[sup -1] leads to fluorescence from the 7Q[sup -*] anion clusters at 22 500 cm[sup -1] with τ[sub fl]=14–27 ns, and also to fluorescence emission from 7KQ[sup *] clusters at 18 370 cm[sup -1] with τ[sub fl]≈7 ns, signaling excited state anion→keto proton transfer. The 25 000 cm[sup -1] absorption band is characteristic of ground state 7KQ, implying that the n>=5 clusters also undergo ground state enol→keto tautomerization. © 2003 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Mass- and isomer-selected S[SUB1]←S[SUB0] resonant two-photon ionization and S[SUB1]→S[SUB0] fluorescence spectra were measured for the 7-hydroxyquinoline·(NH[SUB3])[SUB2] [7HQ·(NH[SUB3])[SUB2]] and d[SUB2]-7-hydroxyquinoline ·(ND[SUB3])[SUB2] clusters cooled in supersonic expansions. UV/UV hole burning measurements prove that a single cluster isomer is formed. Ab initio self-consistent field and density functional calculations predict that the most stable cluster form has an ''ammonia wire'' hydrogen bonded to the -OH and N groups of the cis-7HQ rotamer. The experimental S[SUB0] and S[SUB1] frequencies are in very good agreement with the calculated normal mode frequencies for both the normal and deuterated ammonia-wire clusters. S[SUB1]←S[SUB0] excitation leads to contractions of the -O-H...N and NH[SUB3]...NH[SUB3] hydrogen bonds, as well as smaller displacements for the NH[SUB3]...N(quinoline) stretch and the in plane rotation (or bend) of the ammonia dimer relative to 7HQ. The coupling of these modes to the S[SUB1]←S[SUB0] electronic excitation indicates that hydrogen bond contractions in the excited state are important and may be prerequisite for the S[SUB1] state proton transfer processes that occur in the larger 7HQ· (NH[SUB3])[SUBn] (n≥4) clusters. The calculated electron density differences upon S[SUB1]←S[SUB0] excitation show large π-electron flows on the 7HQ moiety. However, the σ-electronic rearrangements that directly drive the hydrogen bond rearrangements are one to two orders of magnitude smaller. [ABSTRACT FROM AUTHOR]

In the Cage[1] isomer of the water hexamer, the free O-H bonds of the two end-cap water molecules can flip between "up" (u) and "down" (d) orientations, giving four conformers denoted uu, ud, du, and dd. Using the Møller-Plesset second order perturbation method and large basis sets, we calculate fully relaxed potential energy curves as a function of both u↔d torsional angles, denoted φ[SUB1], φ[SUB2]. These predict du as the lowest conformer, with uu nearly degenerate and ud and dd at 30-40 and 50- 70 cm[SUP-1] higher energy, respectively. Along φ[SUB1] the torsional barriers are about 200 cm[SUP-1], along φSUB1]. The torsional zero-point energies are high, the φ[SUB2] between 80 and 110 cm vibrational ground states are strongly delocalized and averaging of the cluster properties is important along both φ[SUB1] and φ[SUB2]. The dipole moment components vary strongly along both φ[SUB1] and φ[SUB2]: μ[SUBa] changes from +0.8 to +2.2 D, μ[SUBb] from +0.5 to +1.2 D, and μ[SUBc] from +1.4 to -0.9 D. The φ[SUB2] torsional fundamental of H[SUB2]O[SUB6] is predicted in the range 65- 72 cm[SUP1] with an intensity of &ap;0.5 D[SUP2],theφ[SUP1] fundamental is in the 22- 32 cm[SUP-1] range, with an intensity of &ap;0.3 D[SUP2]. Both excitations are b/c hybrid perpendicular bands with a dominant b component. The torsional overtones should be very weak. [ABSTRACT FROM AUTHOR]

The structure of the 1-naphthol (NH[SUB3])[SUB2] cluster was investigated by rotational coherence spectroscopy (RCS), mass selective one- and two-color resonant two-photon ionization (R2PI) experiments and ab initio calculations. RCS measurements yielded rotational constants of 1-naphthol (NH[SUB3])[SUB2] as A = 1197, B = 500, and C = 413 MHz, as well as those for several isotopomers. The counterpoise-corrected second-order Mφller-Plesset perturbation theory (MP2) method predicts two isomers A and B. Both structures have hydrogen bonded naphthol-OH… NH[SUB3]… (NH[SUB3] chains, with the second NH[SUB3] (bent above the proximal aromatic ring and pointing towards the p-electron system and have nearly the same binding energy. The experimental rotational constants agree better with those calculated for structure B. The B3LYP and PW91 density functional methods also predict two isomers A, B with the rotational constants of B in acceptable agreement with experiment. Based on two-color R2PI experiments using low ionization frequency to suppress cluster fragmentation, the S[SUB1]←S[SUB0] electronic origin region of the 1-naphthol (NH[SUB3])] [SUB2 - 4] cluster series as reassigned, in agreement with the work of Dedonder-Lardeux et al. [Phys. Chem. Chem. Phys. 3, 4316 (2001)]. In one-color experiments, the 1-naphthol (NH[SUB3])[SUB3] cluster fragments with nearly 100% efficiency into the 1-naphthol (NH[SUB3])[SUB2SUP+] mass channel. [ABSTRACT FROM AUTHOR]

We present an ab initio theoretical study of five low-energy isomers of the water hexamer {Chair, Cage(du)[1], Book, Prism, and Boat}, their intramolecular vibrations, binding energies De and dissociation energies D[sub 0]. Møller-Plesset second order perturbation calculations using the aug-cc-pVTZ basis set at aug-cc-pVDZ optimized geometries including vibrational zero point energy corrections predict Chair to be the most stable isomer, followed closely by Cage(du)[1] (+0.02 kcal/mol) and Book (+0.05 kcal/mol), while Prism is 0.15 kcal/mol higher. The Boat conformer is least stable at both the De and DO levels. The main focus is on the intramolecular normal modes of the five isomers. The calculated O-H stretching frequencies and intensities are compared to recent infrared spectra of water hexamer in supersonic jets, liquid-helium droplets and solid para-hydrogen matrices. The IR spectra indicate that Book and Chair are major species in the latter two environments and may also exist in supersonic jets. The (H[sub 2]O)[sub 6] gas phase interconversion equilibria are calculated and predict that the most abundant isomer is Chair below 8 K, Cage between 8-26 K, and Book above 26 K. Several of the low-frequency vibrational modes are identified as low-amplitude precursors of the Chair+-+Book ↔ Cage isomerization pathways. [ABSTRACT FROM AUTHOR]

The S[sub 1]↔S[sub 0] and S[sub 2]↔S[sub 0] vibronic spectra of the supersonically cooled 2-pyridone dimer (2PY)[sub 2] and its [sup 13]C-, d[sub 1]-, and d[sub 2]-isotopomers were investigated by two-color resonant two-photon ionization and fluorescence spectroscopies. For the C[sub 2h] symmetric (2PY)[sub 2]–h[sub 2] and (2PY)[sub 2]–d[sub 2] complexes, the 2PY moieties are equivalent and the S[sub 1]↔S[sub 0] ([sup 1]A[sub g]↔[sup 1]A[sub g]) transition is forbidden. A single H/D or [sup 12]C/[sup 13]C isotopic substitution reduces the symmetry to C[sub s], so that (2PY)[sub 2]–[sup 13]C and (2PY)[sub 2]–d[sub 1] both exhibit S[sub 1]↔S[sub 0] and S[sub 2]↔S[sub 0] transitions. The S[sub 1]/S[sub 2] state exciton splittings are 43.6 cm[sup -1] and 52.4 cm[sup -1], respectively. These are analyzed in terms of a Frenkel model and compared to calculated splittings based on ab initio monomer transition dipole moments. For (2PY)[sub 2]–d[sub 1], whose 2PY subunits are different, an excitation transfer time of 318 fs is calculated from the exciton splitting. The S[sub 1]↔S[sub 0] and S[sub 2]↔S[sub 0] spectra are analyzed and assigned. Several b[sub u] intermolecular vibrations of S[sub 1] appear via vibronic coupling to the S[sub 2](B[sub u]) state. Combination of the fluorescence data from excitation of the S[sub 1] and S[sub 2] origins and vibrational excitations of (2PY)[sub 2]–h[sub 2], (2PY)[sub 2]–d[sub 1], and (2PY)[sub 2]–d[sub 2] allows the determination of the six S[sub 0] state intermolecular vibrational frequencies.© 2002 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Accurate O–H...O hydrogen-bond dissociation energies were measured for the supersonic-jet-cooled complexes 1-naphthol·S with S=D[sub 2]O, ethanol, oxirane, and oxetane. A mass-selective pump–dump–probe method was used, combining stimulated emission pumping with resonant two-photon ionization and ion-dip techniques. The ground-state dissociation energies D[sub 0](S[sub 0]) are 5.83±0.13 kcal/mol for d[sub 1]-1-naphthol·D[sub 2]O, 7.94±0.02 kcal/mol for 1-naphthol·ethanol, 7.71±0.14 kcal/mol for 1-naphthol·oxirane and >8.17 kcal/mol for 1-naphthol·oxetane. The D[sub 0]’s increase by 5%–7% upon excitation of 1-naphthol to the S[sub 1] state. These dissociation energies are compared to those of the analogous complexes with S=H[sub 2]O, methanol, NH[sub 3], and ND[sub 3] [Chem. Phys. Lett. 246, 291 (1996)]. The trends in D[sub 0] are compared to the electric dipole moments μ, molecular polarizabilities α¯, and gas-phase proton affinities of the H bond acceptor molecules. For the O-containing acceptors, the D[sub 0]’s correlate well with α¯, but the only good overall correlation for both O- and N-containing acceptors was found between the dissociation energies and proton affinities. © 2002 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Hydrogen-bonded complexes of the photoacid 1-naphthol with NH[sub 3] and ND[sub 3] were investigated by resonant two-photon ionization, spectral hole burning, and fluorescence spectroscopies. Although the intermolecular vibrations are weak in both absorption and emission, with typical Franck–Condon factors <2% relative to the electronic origin, all six intermolecular modes were identified, namely the hydrogen bond stretch σ, the ammonia torsion τ, two in-plane wags β[sub 1] and β[sub 2], and two out-of-plane rocking motions ρ[sub 1] and ρ[sub 2]. Several ammonia torsional excitations were observed, with spacings in good agreement with the S[sub 0]- and S[sub 1] state effective torsional barriers derived by Humphrey and Pratt [J. Chem. Phys. 104, 8332 (1996)]. The β[sub 1], β[sub 2], and ρ[sub 2] vibrational excitations exhibit large (2–8 cm[sup -1]) torsional splittings, which indicate strong anharmonic coupling with the ammonia internal rotation. The observed Franck–Condon factors of the intermolecular stretching vibration imply a contraction of the O–H···N hydrogen bond by approx. 0.01 Å upon S[sub 1]←S[sub 0] excitation. © 2001 American Institute of Physics. [ABSTRACT FROM AUTHOR]

Investigates the coupling of a Jahn-Teller pseudorotation in a 9-hydroxytriptycene molecule. Interpretation of the triptycene spectra; Quantification of potential energy surfaces of vibrational modes; Interaction between Jahn-Teller and torsional potentials.

Presents the calculation of a four-dimensional torsional potential for the cyclic water tetramer using high-level ab initio methods. Use of the Gaussian basis set; Calculations of ab initio in the asymmetric unit of the torsional space; Representation of the symmetry relationships between sets of degenerate stationary points and interconversion pathways.

The intermolecular potential energy surface and the torsional-puckering (TP) motion of the cyclic homodromic water pentamer were theoretically investigated at the level of second-order MoilerPlesset perturbation theory using double- and triple-zeta correlation-consistent basis sets including diffuse functions. Extensive searches yielded three cyclic homodromic stationary points: (i) the puckered global minimum structure GS, (ii) a torsional-puckering saddle point, 62 cm[SUP-1] higher, denoted TS1, and (iii) a planar C[SUB5h] symmetric structure (Hessian index 7), 800 cm[SUP-1] higher in energy. Harmonic vibrational frequencies and normal modes were calculated for all stationary points. Based on the energies and second derivatives of the GS and TS 1 structures a cyclic minimum energy path for the large-amplitude TP motion with ten permutationally equivalent minima was constructed. The ground and all excited states are delocalized by TP pseudorotation, giving vibrationally averaged C[SUB5h] symmetry. The first pseudorotational TP level lies at ≈1 cm[SUP-1] (≈0.6 cm[SUP-1]) and the ten lowest TP states within a band of ≈20 cm[SUP-1] (8 cm[SUP-1]) for (H[SUP2]O)[SUB5] [(D[SUB2]O)[SUB5]]. The corresponding TP dipole moment functions were also calculated, and intensities for the far-infrared torsional-puckering transitions of (H[SUB2]O)[SUB5] and (D[SUB2]O)[SUB5] evaluated up to 300 cm[SUP-1]. [ABSTRACT FROM AUTHOR]

We report a combined experimental and theoretical study of the van der Waals isomers and intermolecular vibrations of the 2,3-dimethylnaphthalene·Ne complex in the S1 electronic state. The two-color resonant two-photon ionization spectrum exhibits eight bands within ≊40 cm-1 of the electronic origin. Theoretical considerations in combination with hole-burning spectroscopic measurements show that the transition closest to the electronic origin (at 000+5 cm-1) arises from an isomer which is different from that responsible for the other seven bands in the spectrum. The latter involve excitations of the intermolecular vibrations of the main isomer of 2,3-dimethylnaphthalene·Ne. Accurate three-dimensional quantum calculations of the van der Waals vibrational levels of the complex were performed using a discrete variable representation method. Combination of theory and experiment led to a complete assignment as well as to a quantitative theoretical reproduction of the experimental intermolecular vibrational level structure, and a parametrization of the intermolecular potential energy surface, modeled as sum of atom–atom Lennard-Jones pair potentials. This potential surface exhibits a global minimum above (and below) the aromatic ring plane of 2,3-dimethylnaphthalene and a shallower local minimum at C2v geometry, on the C2 axis of the molecule, adjacent to the two methyl groups. The main and minor isomers identified experimentally are associated with the global and the local minimum, respectively. The quantum calculations were extended to ≊1000 van der Waals vibrational states, i.e., to energies up to 78% of D0. These include levels localized either in the global or local minima, as well as highly excited vibrational states delocalized over all three potential minima, providing comprehensive insight into the quantum dynamics of the high-lying van der Waals states of an atom–large aromatic molecule complex. © 1995 American... [ABSTRACT FROM AUTHOR]

We report a detailed experimental and theoretical study of the intermolecular vibrational levels of the 1,2-dimethylnaphthalene·Ar van der Waals complex in the S1 electronic state. Due to the low symmetry of the aromatic molecular substrate, excitations in all three van der Waals modes (two in-plane, one out-of-plane) are allowed in the electronic spectrum, leading to the most complete data set of intermolecular vibrational transitions measured so far for an atom-large molecule complex. Two-color resonant two-photon ionization spectra reveal twelve bands within ≊95 cm-1 of the electronic origin. Accurate quantum three-dimensional calculations of the van der Waals vibrational levels were performed, using a method based on the 3D discrete variable representation. Combination of theory and experiment allowed a complete and quantitative interpretation of the level structure, as well as an accurate parametrization of the intermolecular potential energy surface (PES), modeled as sum of atom–atom Lennard-Jones pair potentials. The parametrization was partly transferable from other aromatic molecules, but methyl group parameters had to be adapted. Quantum number assignments of the vibrational states were possible for the low-lying levels, but difficult or impossible for states at higher energies, due to strong mode coupling, mainly between the two in-plane modes. © 1995 American Institute of Physics. [ABSTRACT FROM AUTHOR]

A spectroscopic study of supersonic jet-cooled catechol (1,2-dihydroxybenzene) and its d1- and d2-isotopomers, deuterated at the hydroxy groups, was performed by resonant two-photon ionization (R2PI) and fluorescence emission techniques, and supplemented by molecular-beam hole-burning experiments. The latter prove that one single rotamer of catechol is dominant under molecular beam conditions. The complicated vibrational structure in the S0→S1 spectrum from the 000 band to 400 cm-1 above is not due to three different rotamers, as previously thought, but is due to the excitation of a vibrational progression associated mainly with the torsion of the hydroxy groups. The torsional bands are very prominent in the R2PI spectra, but are weak in the emission spectra. Detailed analysis of the torsional bands was based on a fit to the S1 and S0 state frequencies and the Franck–Condon factors in absorption and emission, using a double-minimum potential for the S1 state and a harmonic potential for the S0 state. In the S1 state one of the two –O–H torsional mode frequencies is lowered from τ2≊250 to ≊50 cm-1, and the molecule is only quasiplanar with respect to the –O–H torsional coordinates. [ABSTRACT FROM AUTHOR]

A combined experimental and theoretical study of the intermolecular vibrations of the o-xylene·Ar van der Waals complex is reported for both the S0 and S1 electronic states. Two-color resonant two-photon ionization and fluorescence emission spectra of the vdW mode region of supersonic jet-cooled o-xylene·Ar exhibit five bands within 70 cm-1 of the electronic origin, which arise from low-frequency large-amplitude intermolecular vibrations. Accurate quantum 3D calculations of vdW vibrational levels were performed, based on the 3D discrete variable representation. Apart from the restriction to the J=0 state the calculated eigenstates are exact for the intermolecular potential energy surface (PES) employed. The PES is represented as a sum of Lennard-Jones (LJ) pair potentials, and the direct comparison between theory and experiment enabled calibration of the LJ parameters. Very good agreement was achieved for both the S0 and S1 states of o-xylene·Ar. The quantum 3D calculations provide a quantitative description of the vdW level structure up to ≊70 cm-1 above the vdW ground state. The low-energy eigenfunctions have nodal patterns analogous to the 2,3-dimethylnaphthalene·Ar complex. However, in the energy range 40–60 cm-1 the vdW mode eigenfunctions change over to 2D radial-oscillator-type wave functions, similar to those of benzene·Ar, but switch back to Cartesian type above 60 cm-1. The S1 state vdW levels of 2,3-dimethylnaphthalene [M. Mandziuk, Z. Bacˇic, T. Droz, and S. Leutwyler, J. Chem. Phys. 100, 52 (1994)] were recalculated with the present parameters, and the agreement between experimental and calculated frequencies is improved. [ABSTRACT FROM AUTHOR]

The effect of rare gas complexation on the electronically excited S1(E’) state of triptycene (T), which is Jahn–Teller distorted, was investigated by two-color resonant two-photon ionization (2C-R2PI) spectroscopy of the supersonically cooled van der Waals complexes triptycene·Nen, n=1–3. These complexes afford unique possibilities to study the effects of weak intermolecular interactions on the intramolecular Jahn–Teller coupling. Since the atoms are adsorbed at high-symmetry positions, the system symmetry is lowered from D3h(n=0) to C2v for n=1 and 2, but reverts to D3h for n=3. A Jahn–Teller (A1+E)xe coupling model including a uniaxial external strain component was applied successfully to calculate the S1 state levels and S1←S0 electronic spectra of all three complexes. The spectrum of T·Ne3 was fully interpreted without inclusion of strain, implying a highly symmetric D3h structure in which each of the three V-shaped compartments of triptycene is occupied by a single Ne atom. In contrast, the vibronic spectra of T·Ne and T·Ne2 were fitted with a considerable uniaxial strain of -19.73 and 19.07 cm-1, respectively, confirming both the predicted C2v geometry of the complexes as well as the equal magnitude, but opposite sign of the intramolecular distortion induced by one or two Ne atoms. These distortions correspond to a small change of the angle of the V-shaped compartments by ∼0.8°. The spectra of T·Ne and T·Ne2 are much more complex compared to triptycene and T·Ne3 due to the splitting of the E vibronic levels in C2v symmetry, and the appearance of additional transitions to levels that are weak or symmetry forbidden in bare triptycene. The calculated Jahn–Teller potential energy surfaces and vibronic wave functions are discussed and classified in terms of their symmetry and localization/delocalization properties. [ABSTRACT FROM AUTHOR]

The vibronic structure in the S1(E)←S0(A1) resonant two-photon ionization (R2PI) spectrum of supersonically cooled 9-fluorotriptycene is assigned using three different Jahn–Teller (JT) model Hamiltonians for the excited 1E state—Exe, (A+E)xe, and (A+E)x(a2+e). The basic Exe interpretation is satisfactory. However, the fitted vibronic band frequencies and intensities are improved by including coupling to a second excited state 1A1 in an exciton model. Some further observed absorption bands are only assignable by invoking a molecular Barnett effect (momentum coupling to an a2 vibration). The measured fluorescence emission spectra from different S1 vibronic levels are quantitatively reproduced within all three coupling schemes by the parameters fitted to the R2PI spectrum. Results are compared to previous calculations on unsubstituted triptycene. The JT stabilization energy is decreased by ∼10% upon fluoro bridgehead substitution, which is rationalized by the electron-withdrawing effect of the F atom. For the same reason, the exciton splitting between the S1 and the S2 states, as calculated in the (A+E)xe model, is reduced relative to triptycene. The ground state vibrational frequencies in the range 0–700 cm-1 are calculated using the semiempirical MOPAC 6.0/AM1 method and compared with the measured S0 frequencies, as well as those of triptycene. A 273 cm-1 degenerate C–F bending mode predicted by the AM1 calculation may explain several unassigned features in the higher-energy (200–360 cm-1) part of the R2PI spectrum, and may represent an example of e+e multimode coupling within a degenerate electronic state. [ABSTRACT FROM AUTHOR]

Molecular dynamics simulations were performed for van der Waals clusters naphthalene·Arn, n=1 to 4. For all isomers and conformers of these clusters, dynamical quantities such as velocity autocorrelation functions, vibrational power spectra, and semiclassical electronic absorption spectra were calculated over a wide energy range, and averaged over a canonical distribution at temperatures in the range T=5 to 30 K. Electronic absorption spectra were calculated for the origin bands according to the semiclassical method [L. E. Fried and S. Mukamel, J. Chem. Phys. 96, 116 (1992)] and are compared with the corresponding experimental naphthalene·Arn R2PI spectra [T. Troxler and S. Leutwyler, J. Chem. Phys. 95, 4010 (1991)]. The appearance of distinct absorption bands due to specific isomers for a given cluster size, as observed experimentally, is well reproduced by the simulations. Comparison of calculated electronic shifts for different isomers allows clear assignments in the experimental spectra. Increasing the simulation temperature to T=15–25 K is accompanied by band broadening and the appearance of sidebands towards the blue. Especially strong sidebands appear for naph·Ar2 and all clusters containing the Ar2 subunit, due to large-amplitude surface rotation/translation of the argon dimer on the naphthalene surface, in agreement with experiment. For clusters containing the n=3 and n=4 subunits the spectral broadening is smaller. For the n=4 (4+0)-isomer, the calculated band shape increases less than for the other n=4 isomers, mainly due to the motional narrowing effect of cluster fluxionality. Above 25 K, isomerization between different possible topological structures also occurs by side-crossing motion of one or several argon atoms. [ABSTRACT FROM AUTHOR]

Van der Waals (vdW) clusters of naphthalene with argon were synthesized in supersonic beam expansions. Mass-selective absorption spectroscopy was carried out by using fragmentation-free two-color resonant two-photon ionization with mass-spectrometric detection. Electronic spectra of naph·Arn (n≤6) were recorded at the vicinity of the naphthalene S1←S0 electronic origin (32 020 cm-1 ), and corresponding spectra for the 810 transition up to n=30. For n=3, the spectra due to two different isomers could be separated. Clear evidence for the existence of different cluster isomers was also found for n=6, 8, 9, 12–14, and 25–28. In comparison with most other solvent clusters M·Arn (M is the aromatic molecule), the spectral red shifts of 000 and vibronic bands of the naph·Arn clusters are very small. Analysis of the size dependence of the electronic spectral shifts indicates that the stepwise solvation of the naphthalene molecule proceeds predominantly on one side of the molecule. Two semicyclic trends in the spectral shifts are interpreted as successive wetting-nonwetting transitions which occur with increasing solvent cluster size. In the proposed mechanism for these transitions, part of the innermost solvent layer ‘‘unwets’’ the substrate, and moves to the second or third layer, thereby forming a nonwetting dropletlike cluster on one side of the naphthalene substrate. [ABSTRACT FROM AUTHOR]

Excited-state proton transfer from 1-naphthol to water was studied as a function of solvent system size, from supersonically cooled neutral clusters, 1-naphthol·(H2O)n, n=1–50, to bulk ice and water. Occurrence or nonoccurrence of proton transfer was detected and studied using cluster-size-specific laser-spectroscopic techniques: resonant two-photon ionization (R2PI) and laser-induced fluorescence emission. Depending on cluster size or solution phase, three qualitatively different types of excited-state behavior were observed: (1) For small clusters, n≤7, both the R2PI and fluorescence spectra of the clusters were similar in nature to the spectra of bare 1-naphthol; (2) the medium-size clusters (n=8–20) show incremental spectral shifts which indicate successive stages of molecular solvation, and the spectra approach that of 1-naphthol in bulk ice at n≊20; (3) the fluorescence spectra for large clusters, n≥20, show increasing emission intensity below 25 000 cm-1, characteristic of the emission of the excited-state 1-naphtholate anion. Excited-state proton transfer appears to occur in the largest observed clusters (n≥30), yet the fluorescence spectra do not converge fully to that of 1-naphtholate anion in bulk water. These three behaviors are discussed in terms of a model based on three distinct excited states connected by two electronic and geometric rearrangement processes. The model accounts in a unified way for the complete range of aqueous solvation behavior observed here as well as in many other solvent systems studied previously. The extent of proton transfer reaction is largely solvent controlled, the major determinants being the proton affinity of the solvent or solvent cluster, and its ability to resolvate the nascent ion pair on a subnanosecond time scale. In bulk ice, the slow solvent relaxation results in complete absence of excited-state proton transfer from both 1- and 2-naphthol. [ABSTRACT FROM AUTHOR]

Efficient excited-state proton transfer in neutral acid–base clusters α-naphthol·Bn has been detected and studied by a combination of laser spectroscopic techniques (resonant two-photon ionization, fluorescence excitation, and emission spectroscopy). S1 state proton transfer was observed for B=NH3 and n≥4, as evidenced by several criteria: (a) large red shift and substantial broadening of the R2PI spectra of the n≥4 clusters relative to those of the bare α-naphthol and smaller clusters; (b) very large Stokes shift (∼8000 cm-1) of the emission spectra of the n≥4 clusters; (c) complete broadening of the fluorescence emission band for the n≥4 clusters; and (d) a striking similarity of the emission band position and width of the latter spectra to the emission spectrum of the α-naphtholate anion in basic aqueous solution. No proton-transfer reaction was observed for small solvent clusters with B=NH3 and n≤3, nor for any of the pair complexes studied, which involve a single base partner [B=triethylamine, 3-dimethylamino-1-aminopropane, 1,4-bis(dimethylamino)butane] which we have studied so far. This behavior illustrates the difficulty of achieving charge separation in neutral gas-phase complexes or clusters. A critical gas-phase proton affinity PAcrit =248±3 kcal/mol was determined for proton transfer to take place in the α-naphthol·Bn (or base B) system. [ABSTRACT FROM AUTHOR]

The structures, binding energies, and vibrational frequencies of fully optimized water clusters (H2O)n, n=1– 4, were computed with ab initio molecular orbital theory at the SCF level using different basis sets. The SCF procedure allows satisfactory predictions for these properties compared with experimental results. For quantitative predictions of binding energies and geometrical parameters, a basis set including polarization functions is needed. With respect to intramolecular vibrational frequencies and frequency shifts, however, the split valence basis set 4-31G leads in all cases to the best rationalization of the available experimental data. Analysis of intramolecular force constants, frequencies, and eigenvectors for n=2 to 4 shows that (i) a transition from highly localized (n=2) to highly delocalized (n=4) vibrational modes takes place; (ii) the delocalized O–H vibrations of cyclic (H2O)n clusters (n≥3) can be described as longitudinal/transverse optical phonons; (iii) internal force constants for the hydrogen bonding O–H stretch, k(O–Hb), decrease strongly with size, leading to a decrease in the νbridge O–H frequencies; a similar decrease is found for the intramolecular bending force constant k(Θ); (iv) force constants for the free O–H stretching motions k(O–Hf) stay nearly constant, as do the corresponding vibrational frequencies; (v) intermolecular stretch–stretch couplings increase substantially with n and dominate over intramolecular stretch–stretch couplings for n≥3; similarly, intermolecular bend–libration couplings are very important. [ABSTRACT FROM AUTHOR]