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The available experimental data provided by ultrafast dynamics studies of pyrrole and its derivatives in excited states of mixed Rydberg/valence 3s/πσ* character are strongly affected by the interaction with the laser pulses. Understanding these data has constituted an endeavor for several groups during the past few years. Here we apply a simple theoretical model that, including the interaction with the laser pulses, allows one to clarify some aspects of the discrepancies between measurements monitoring different experimental observables. New experimental data on pyrrole, 2,4-dimethylpyrrole, and 2,5-dimethylpyrrole are also provided to check the validity of the model and to gain more insight into the excited state dynamics of pyrrole systems.

We have investigated the relaxation, following excitation in the 290–235 nm region, of neutral aniline homoclusters (An)n formed in a supersonic expansion by femtosecond time resolved ionization. The applied method permits isolation of the dynamics of the dimer from that originated in bigger species of the generated distribution. Interestingly, and differently from the monomer and (An)n≥3 clusters, the dimer does not present a N–H dissociative 1πσ* channel. This fact can be explained in terms of the symmetric structure adopted, in which each molecule establishes two N–H⋯π interactions, destabilizing the H dissociation channel. The observations permit relating the photophysics to the interactions established by the aniline units and confirming previous observations and theoretical predictions on the structure of aniline aggregates.

The relaxation dynamics of thiophenol, excited from the onset of the S 1 (1 1 ππ ∗ ) state absorption, to the more intense S 3 (2 1 ππ ∗ ) state band (290–244 nm), has been studied by time resolved ion yield spectroscopy. Along the studied energy range, the reached excited states relax in less 100 fs. These results evidence that the photophysics is dominated by the non-adiabatic coupling between the initially excited S 1 and S 3 1 ππ ∗ states, and the dissociative character 1 πσ ∗ state. Contrarily to phenol, the 1 1 ππ ∗ / 1 πσ ∗ crossing is reached from the origin of the 1 1 ππ ∗ state absorption, through a nearly barrierless pathway.

International audience; A complete photophysical study on the iodinated-BODIPY, 3,5-dimethyl-2,6-diiodo-8-thiomethyl-pyrromethene (MeSBDP), demonstrated that it is an excellent triplet photosensitizer for singlet oxygen production in a broad range of apolar and polar solvents. Besides its absorption and fluorescence emission spectra, the dynamics of its excited states including its intersystem crossing rate was characterized by femtosecond transient experiments. The photophysical study of its triplet state by nanosecond transient absorption spectroscopy and phosphorescence emission concluded to a diffusion-controlled quenching of 3MeSBDP by O2 and to a fraction of triplet state quenching by O2 Image ID:c9cp03454d-t1.gif close to unity. The high (>0.87) and solvent-insensitive singlet oxygen quantum yield ϕΔ measured by singlet oxygen phosphorescence emission, together with the noticeable photostability of MeSBSP, as well as the absence of quenching of singlet oxygen by MeSBDP itself, allows claiming it as an alternative standard photosensitizer for singlet oxygen production, under excitation either in the UV or in the visible range.

The photodynamics of an orthogonal BODIPY dimer, particularly the formation of triplet states, has been explored by femtosecond and nanosecond transient absorption measurements. The short time scale data show the appearance of transient features of triplet character that, according to quantitative analysis of their intensities, account for more than 100% of the initially excited molecules, which reveals the occurrence of a singlet fission process in the isolated dimers. The formation rate of the triplet correlated state (TT) is found to depend on the solvent polarity, pointing to the mediation of a charge transfer character state. The dissociation of the (TT) state into pairs of individual triplets determines the triplet yield measured in the long time scales. The kinetic model derived from the results provides a comprehensive view of the photodynamics of BODIPY dimers and permits rationalization of the photophysical parameters of these systems.

Micelles are interesting self-organized structures with multiple applications in chemistry and related with the formation of biological structures. Their final shape depends on a subtle equilibrium between several weak forces: namely, van der Waals and hydrogen bond interactions. In order to address the influence of each type of interaction, the aggregation of cyclohexanol molecules was studied in the gas phase. The geometry of the clusters formed with sizes from 2 to 6 cyclohexanol molecules was elucidated by an IR double resonance technique that combines fs and ns lasers. Comparison of the structures obtained with those from previous studies demonstrates that hydrogen bond plays a central role in defining the general shape, but that its contribution to the overall stabilization energy may be lower than expected in systems with multiple C-H···π interactions.

The photochemical and photophysical pathways operative in N-methylpyrrole, after excitation in the near part of its ultraviolet absorption spectrum, have been investigated by the combination of time-resolved total ion yield and photoelectron spectroscopies with high-level ab initio calculations. The results collected are remarkably different from the observations made for pyrrole and other aromatic systems, whose dynamics is dictated by the presence of πσ* excitations on X–H (X: N, O, S, ...) bonds. The presence of a barrier along the C–N dissociation coordinate that can not be tunneled triggers two alternative decay mechanisms for the S1 A″ πσ* state. While at low vibrational content the C–N dissociation occurs on the surface of a lower 3ππ* state reached after efficient intersystem crossing, at higher excitation energies, the A″ πσ* directly internally converts to the ground state through a ring-twisted S1/S0 conical intersection. The findings explain previous observations on the molecule and may be relevant for more complex systems containing similar C–N bonds, such as the DNA nucleotides This work was funded by the “Ayudas para apoyar las actividades de grupos de investigación del sistema universitario vasco” program from the Basque Government, Grant 2014SGR1202 from the Agència de Gestiód’Ajuts Universitaris i de Recerca (AGAUR) from Catalonia (Spain), CTQ2016-69363-P from the Spanish Ministerio de Economıá y Competitividad (MINECO) and UNGI10-4E-801 from the Ministerio de Ciencia e Innovación (MICINN) and the European Fund for Regional Development, and the Xarxa de Refereǹ cia en Quiḿ ica Teor̀ ica i Computacional de Catalunya (AGAUR)

Mass-resolved excitation spectroscopic techniques are usually limited to systems with a chromophore, that is, a functional group with electronic transitions in the Vis/UV, with lifetimes from hundreds of picoseconds to some microseconds. In this paper, we expand such techniques to any system, by using a combination of nanosecond IR pulses with nonresonant ionization with 800 nm femtosecond laser pulses. Furthermore, we demonstrate that the technique can achieve conformational specificity introducing an additional nanosecond IR laser. As a proof-of-principle, we apply the technique to the study of phenol(H(2)O)(1), propofol(H(2)O)(1) γ-butyrolactone(H(2)O)(n), n = 1-3, and (H(2)O)(2) complexes. While monohydrated phenol and propofol clusters permit a direct comparison with a well-studied system including an aromatic chromophore, γ-butyrolactone is a cyclic nonaromatic molecule, whose mass-resolved spectroscopy cannot be tackled by conventional techniques. Finally, we further demonstrate the potential of the technique by obtaining the first mass-resolved IR spectrum of the neutral water dimer, a nice example of a system whose ionization-based detection had not been possible to date.

The influence of water solvation on the photophysics of the indole chromophore has been investigated by revisiting the ultrafast relaxation of indole–water clusters. The dynamics after excitation in the 284–234 nm energy range has been tracked by time delayed ionization with a 1305 nm probe. The results collected in the indole– ( H 2 O ) 1 + mass channel, which were ascribed mainly to the indole– ( H 2 O ) 2 + cluster fragmented by dissociative ionization, reflect a dynamical behavior analogous to that observed for the isolated indole molecule. The two femtosecond time constants observed in the transients were assigned to the coupling between the L a and L b π π ∗ surfaces, and to the system evolution along the dissociative π σ ∗ state.

The relaxation dynamics of the isolated indole molecule has been tracked by femtosecond time-resolved ionization. The excitation region explored (283-243 nm) covers three excited states: the two ππ* L(b) and L(a) states, and the dark πσ* state with dissociative character. In the low energy region (λ273 nm) the transients collected reflect the absorption of the long living L(b) state. The L(a) state is met 1000-1500 cm(-1) above the L(b) origin, giving rise to an ultrafast lifetime of 40 fs caused by the internal conversion to the lower L(b) minimum through a conical intersection. An additional ~400 fs component, found at excitation wavelengths shorter than 263 nm, is ascribed to dynamics along the πσ* state, which is likely populated through coupling to the photoexcited L(a) state. The study provides a general view of the indole photophysics, which is driven by the interplay between these three excited surfaces and the ground state.

An experimental study of the evolution of nanosecond pulsed lasers absorbed by Ni metal is presented. The ions ejected near fluence threshold fit single Maxwell–Boltzmann distributions (MBDs) whereas the ion distributions at higher fluences have side-bands whose maxima match accurately those of the ionization and recombination precursors. It is demonstrated that ions are trapped for ≈1 μs and further ejected in a few picoseconds whereas electrons have shorter dead time (≈10 ns) and continue evaporating for as long as ≈1 μs. Radiation is partially trapped during the creation of the electric field that ejects ions. The evolution also applies to other metals.

The relaxation dynamics of naphthalene (NPH) and 1-aminonaphthalene (AMN) in superexcited (SE) states has been investigated by pump-probe femtosecond ionization. SE states were produced by two-photon resonant absorption via S1 and S2 states and their time evolution probed by ionization with 800 nm light pulses. A fine-tuning of the pump and probe laser intensities permits us to separate the dynamics of the SE states from that of the S1/S2 intermediate states. SE state relaxation pathways were investigated in the channels of the parent and the major fragment ions. The lifetimes of two relaxation processes were derived from the exponential fit and found to be in the femtosecond and the picosecond time scales. The fast component is attributed to internal conversion (IC) from the SE states to the Rydberg states, whereas the slow one, only observed in the fragment transients, is assigned to fragmentation of the relaxed neutral molecules. The study sheds light on the significant role of SE states dynamics in pump-probe ionization experiments.

The relaxation dynamics of jet cooled naphthalene (NPH) has been studied by mass-resolved transient ionization, following excitation to the S 1 (L b ) and S 2 (L a ) states and further single/multi photon ionization at a variety of probe wavelengths. Time-dependent signals were collected from the parent C 10 H 8 + and the C 10 H 7 + fragment ions. The relaxation transients include two lifetimes of 30 and 800 fs. The short decay suggests the presence of a conical intersection nearby the L a state surface minimum that is crossed in one single passage by most part of the population, whereas the long lifetime is tentatively assigned either to internal vibrational redistribution (IVR) within the L b state, or to the decay of coherent recurrences.

A detailed investigation on the ion kinetic energy distributions of ions ejected in the nanosecond pulsed laser ablation of aluminum is reported. For laser fluences just over threshold, the emerging ions fit shifted neat Maxwell−Boltzmann-Coulomb (MBC) distributions. For fluences higher than ∼1.3 J/cm2, the Al+ distributions split into two MBC contributions peaked at different energies. It is demonstrated that the observed Al+ ion distribution has two components, one fast, correlated with the direct multiphoton laser ionization, and the other slow, associated with electron−Al0 collisions in the solid. A similar behavior is observed at higher fluences for all Al ion distributions indicating that the electron-impact ionization of Al rate constants is faster than that of recombination and other possible collision channels. In addition, the linear relationship between the Coulomb velocities and the ion charges and the behavior of Coulomb energy of the ions versus the laser fluence suggest the appearance of an...

The nonradiative relaxation channels of gas-phase tryptophan excited along the S1–S4 excited states (287–217 nm) have been tracked by femtosecond time-resolved ionization. In the low-energy region, λ ≥ 240 nm, the measured transient signals reflect nonadiabatic interactions between the two bright La and Lb states of ππ* character and the dark dissociative πσ* state of the indole NH. The observed dynamical behavior is interpreted in terms of the ultrafast conversion of the prepared La state, which simultaneously populates the fluorescent Lb> and the dissociative πσ* states. At higher energies, after excitation of the S4 state, the tryptophan dynamics diverges from that observed in indole, pointing to the opening of a relaxation channel that could involve states of the amino acid part. The work provides a detailed picture of the processes and electronic states involved in the relaxation of the molecule, after photoexcitation in the near part of its UV absorption spectrum.

The relaxation of 2,5-dimethylpyrrole after excitation in the 290-239 nm range, which covers the weak absorption of the S1 (1)A2 πσ* state, dissociative along the N-H bond, and the stronger band mostly attributed to the (1)B2 ππ* state, has been investigated by time-resolved ion and photoelectron techniques. The measurements yield an invariant lifetime of ∼55 fs for the (1)πσ* state, after preparation in its Franck-Condon region with increasing vibrational content. This ultrafast rate indicates that, contrary to the observations made in pyrrole (Roberts et al. Faraday Discuss. 2013, 163, 95-116), the molecule reaches the dissociative part of the potential without any barrier effect, although calculations predict the latter to be higher than in the pyrrole case. The results are rationalized in terms of a barrier free multidimensional pathway that very likely involves out-of-plane vibrations. Additionally, a lifetime of ∼100 fs is found after excitation along the higher (1)B2 ππ* ← S0 transition. The relaxation of this state by coupling to a very short living S1 (1)πσ* state, or by alternative routes, is discussed in the light of the collected photoelectron measurements.

2-Colour REMPI and ZEKE-PFI spectra of the 4-amino-3-ethylbenzonitrile (EtABN) molecule are reported for the first time. EtABN S 1 ← S 0 0 0 0 transition is located at 33 578 cm −1 , and its adiabatic ionisation threshold, as determined by ZEKE-PFI spectroscopy is 64 799 ± 4 cm −1 . A comparison with the spectra of 4-aminobenzonitrile (ABN) shows that the ethyl substituent gives rise to a rich spectroscopy, mainly involving the Ph–Et rocking mode.

The adiabatic ionization threshold (AIT) of trans- and gauche-benzocaine has been measured by zero electron kinetic energy-pulsed field ionization (ZEKE-PFI) spectroscopy to be 7.8412+/-0.0008 eV (lasers at 34,134.4 and 29,109.3 cm(-1)) and 7.8421+/-0.0004 eV (34,144.8+29105.7 cm(-1)), respectively. AITs computed at the B3LYP/AUG-cc-p-VDZ level for the two conformers are some approximately 2,500 cm(-1) lower than the experimental; in contrast their energy difference is very close. The trans-benzocaine cation ZEKE spectra has been recorded taking a number of S(1) intermediate vibronic states. The spectra provide an energy threshold for the appearance of intramolecular vibrational redistribution (IVR) around approximately 540 cm(-1) in the S(1) state.

The conformational isomerization dynamics of melatonin and 5-methoxy N-acetyltryptophan methyl amide (5-methoxy NATMA) have been studied using the methods of IR-UV hole-filling spectroscopy and IR-induced population transfer spectroscopy. Using these techniques, single conformers of melatonin were excited via a well-defined NH stretch fundamental with an IR pump laser. This excess energy was used to drive conformational isomerization. By carrying out the infrared excitation early in a supersonic expansion, the excited molecules were re-cooled into their zero-point levels, partially re-filling the hole created in the ground state population of the excited conformer, and creating gains in population of the other conformers. These changes in population were detected using laser-induced fluorescence downstream in the expansion via an UV probe laser. The isomerization quantum yields for melatonin show some conformation specificity but no hint of vibrational mode specificity. In 5-methoxy NATMA, no isomerization was observed out of the single conformational well populated in the expansion in the absence of the infrared excitation. In order to study the dependence of the isomerization on the cooling rate, the experimental arrangement was modified so that faster cooling conditions could be studied. In this arrangement, the pump and probe lasers were overlapped in space in the high density region of the expansion, and the time dependence of the zero-point level populations of the conformers was probed following selective excitation of a single conformation. The analysis needed to extract isomerization quantum yields from the timing scans was developed and applied to the melatonin timing scans. Comparison between the frequency and time domain isomerization quantum yields under identical experimental conditions produced similar results. Under fast cooling conditions, the product quantum yields were shifted from their values under standard conditions. The results for melatonin are compared with those for N-acetyl tryptophan methyl amide.

Author Institution: Department of Chemistry, Purdue University; Department of Chemistry and the James Franck Institute, University of Chicago

The 4-aminobenzonitrile (ABN) molecule has two active sites amenable to hydrogen bonding to methanol (MeOH) and ethanol (EtOH): the amino, –NH2, and the cyano, –CN, groups. Two-color resonance enhanced multiphoton ionization time-of-flight mass spectroscopy and hole burning spectroscopy in addition to the ionization energies provides sound evidence of the occurrence of two isomers in the ABN(MeOH)1 complex and one single isomer for the ABN(EtOH)1 complex. Combining the outcomes from the ABN/methanol and ABN/ethanol experiments with ab initio computations at reliable theory levels one identifies the preferred solvation sites and the optimized geometries. A discussion of the role of the aliphatic chains on the geometry of the isomers and other properties is presented.

The electronic and infrared spectra of anthranilic acid in a supersonic jet were measured. The fluorescence excitation spectrum is extremely congested. IR−UV hole-burning measurements indicate that only a single ground-state rotamer contributes to the observed spectrum. Vibrational progressions in 252 and 418 cm-1 modes were observed. Density functional theory calculations indicate that these modes involve the in-plane bending motions of the amino and carboxyl groups of anthranilic acid. The presence of vibrational progressions in these modes suggests that the relative positions of the amino and carboxyl groups are different in the ground and excited electronic states of anthranilic acid. This observation is supported by the fluorescence-dip infrared spectra acquired, which show a shift in the lower frequency NH stretch fundamental from 3394 to 2900 cm-1 upon electronic excitation, suggesting a dramatic strengthening of the intramolecular hydrogen bond in the excited state. The change in the hydrogen-bond...

This work reports the identification of the gas phase amino-p-phenethylamine (APEA) conformers with computed DFT stable structures. Two-colour mass-resolved multiphoton ionisation and hole burning spectroscopies have been used to find the number of conformers and record their spectra. The spectra show the presence of four well-characterized conformers, with origin bands paired off as gauche and anti conformers, in clear contrast to the five stable structures predicted by computational methods. Several criteria have been employed to relate the experimental spectra of the conformers to stable computed structures, the ionisation energies being the most reliable for unambiguous identification. The method can be applied to other small- and medium-size biological and organic molecules.

Herein, the interpretation of the femtosecond-scale temporal evolution of the pyrrole ion signal, after excitation in the 267-217 nm interval, recently published by our group [R. Montero, A. Peralta Conde, V. Ovejas, M. Fernández-Fernández, F. Castaño, J. R. Vázquez de Aldana, and A. Longarte, J. Chem. Phys. 137, 064317 (2012)] is re-visited. The observation of a shift in the pyrrole(+) transient respect to zero delay reference, initially attributed to ultrafast dynamics on the πσ* type state (3s a1 ← π 1a2), is demonstrated to be caused by the existence of pump + probe populated states, along the ionization process. The influence of these resonances in pump-prone ionization experiments, when multi-photon probes are used, and the significance of a proper zero-time reference, is discussed. The possibility of preparing the πσ* state by direct excitation is investigated by collecting 1 + 1 photoelectron spectra, at excitation wavelengths ranging from 255 to 219 nm. No conclusive evidences of ionization through this state are found.

An extensive laser spectroscopic, structural and computational investigation on the neurotransmitter analogue p -methoxyphenethylamine (MPEA) chromophore weakly bound to one molecule of water, (MPEA(H 2 O) 1 ) is reported. The complex was prepared by supersonic expansion of a gas mixture of seeded MPEA and water molecules in rare gas He. Two well-characterised experimental isomers have been observed, with geometries resulting from large contributions of the ordinary hydrogen bond and other intermolecular forces. Four key properties of the complex and related species are addressed in this paper: the characterisation of the isolated isomers observed spectra, the measurements of the binding energies of the ground, first electronic and ground ion states of the complex, the identification of each isomer spectrum with the computed geometries and the relationship of the complex stable isomers with the precursor conformers. A number of mass resolved laser spectroscopies have been used in order to get a complete set of experimental results, that complemented with ab initio density functional computations at four basis set, finally permitted us to settle and assign the mentioned properties of the two observed MPEA(H 2 O) 1 isomers.

Weakly bound complexes of phenol (Ph) and fluoromethane (CH3F) formed in a supersonic expansion have been identified by one- and two-color mass-resolved and hole burning spectroscopies. Only one isomer has been observed for the 1:1 complex. Threshold fragmentation has been employed to determine the binding energies of the complex in its ground, S0, and first electronic, S1, states, as well as in the ion ground state, I0, yielding the following results: D0(S0)=1540±50 cm−1, D0(S1)=1713±50 cm−1, and D0(I0)=3932±50 cm−1, respectively. In a complementary study, calculations on the complex geometries and binding energies were conducted at the B3LYP/6-31+G* and the MP2/6-31+G* levels. It has been shown that the binding energies computed at the MP2/6-31+G* level are in excellent agreement with the experimental values, whilst those calculated at the B3LYP/6-31+G* level underestimate them by nearly 30%, probably due to the poor description of the dispersion forces.

Binding or dissociation energies of the ground state, S0, the first electronic excited state, S1, and the ion ground state, I0, of the p-methoxyphenetylamine(H2O)1-4 complexes, referred to henceforth as either MPEA(H2O)1-4 or by their stoichiometric ratios 1:1−4, have been analyzed by threshold ion fragmentation. MPEA(H2O)1-4 complexes were prepared by the supersonic expansion of premixed samples containing appropriate amounts of MPEA and water molecules into carrier gas He. A number of isomers, with characteristic transition energies, have been identified: two for MPEA(H2O)1 at 35 676 and 35 689 cm-1, one for MPEA(H2O)2 at 35 687, one for MPEA(H2O)3 at 35 571 and two for MPEA(H2O)4 at 35 419 and 35 422 cm-1 respectively. The ionization energy and fragmentation thresholds, the latter defined as the onset energy of the process MPEA(H2O)n* + hν→ MPEA(H2O)n-1+ + H2O, have been determined, and from them the dissociation energies for the set of MPEA(H2O)1-4 isomers in their ground state, first electronic exci...

Weakly bound hydrogen bonded ethyl-p-aminobenzoate/water complexes, referred to henceforth both as EAB/(H2O)n (n=1–4) or by their stoichiometry 1:n, have been investigated with a combined approach of mass and light detector laser spectroscopic techniques and ab initio calculations. The experimental studies follow explorations with laser induced fluorescence (LIF), and include one-color resonant enhanced multiphoton ionization (REMPI), two-color REMPI (R2PI), pressure dependent R2PI and hole burning (HB) spectroscopies. Calculations were conducted at the B3LYP/6-31+G* level and for the 1:1 complex led to the existence of six stable isomers, identified as the experimental origin bands at +4, +6, +13, +89, +96, and +108 cm−1 above the bare EAB 000 transition. It has been shown that three of these bands originate in the EAB trans conformer, while the other three derive from the EAB gauche conformer. None of the experimental methods used lead us to observe the EAB(H2O)2 complex spectrum and the inspection of t...

A combined theoretical and experimental study of ethyl- p -aminobenzoate (EAB) molecule to substantiate the number of conformers, identify their electronic 0 0 0 transitions, vibrational bands, structures and ionisation energies is reported. The experimental study is mainly based on pump–probe laser techniques on the sample molecule prepared in a supersonic expansion beam and includes one-colour and two-colour resonance enhanced multiphoton ionisation (REMPI, R2PI) hole burning and dispersed emission spectroscopies. The spectra are rationalised with the help of density functional theory (DFT) computations at the B3LYP/6-31+G* level. EAB R2PI spectrum is reported for the first time and the trans and gauche conformers ionisation energy thresholds have been measured to be 7.828 and 7.826 eV, respectively. The small energy difference of the trans and gauche 0 0 0 transitions is suggested to be originated in the different contribution of the ethyl group orbitals to the conformer highest and lowest occupied molecular orbital states. Ground and first electronic excited states vibrational spectra of both conformers have been assigned with the help of the computed DFT vibrational wave numbers. The most intense bands of the vibrational spectra are identified as belonging to ring vibrations: 10a, 17b, 1+skeletal vibration, 5, 17a, 18b among others. Most vibrational modes in both conformers appear at close wave numbers and only the low energy modes, in the region below 400 cm −1 , should be regarded as the characteristic fingerprint of each conformer. No long vibrational progressions have been observed.

A combined wide range of laser spectroscopic techniques and computational quantum chemistry are used to investigate conformer landscapes of large substituted aromatic molecules. The spectroscopic techniques include laser-induced fluorescence (LIF), high-resolution LIF, resonance-enhanced multiphoton ionization (REMPI) with mass detection, two-color resonance ionization with mass detection (R2PI), laser dispersed emission (DE), and ion-dip hole burning (HB). These techniques are balanced with extensive ab initio DFT calculations at the B3LYP/6-31+G* and B3LYP/6-311+G* levels. These methods have been applied to investigate the nine possible conformations of the p−methoxyphenethylamine (MPEA) neurotransmitter molecule. Even when all the spectroscopic techniques play important roles, two color ionization energy (IE) threshold determinations have proven to be especially useful in the study. The gauche and anti conformers exhibit different ionization energy values, and even the amino hydrogen orientation influe...

Methyl-p-aminobenzoate(H2O)1 complex, henceforth MAB(H2O)1, prepared by pulsed supersonic expansion, has been examined by a broad range of laser based spectroscopic, mass and isomer selective techniques and density functional theory (DFT) calculations, in order to identify its isomer structures, ionization energies, and vibrational frequencies. The experimental techniques used include laser induced fluorescence (LIF), mass resolved excitation spectroscopy (MRES) either with one (REMPI) or two laser colors (R2PI), laser excited dispersed emission (DE), high resolution MRES, pressure controlled R2PI, hole burning (HB) spectroscopy, and photoion fragmentation threshold (PIFT). Experimental results have been interpreted, rationalized and extended with density functional theory (DFT) computations at the B3LYP/6-31G and B3LYP/6-31+G* levels. Although bare MAB molecule have four possible solvation sites, prone to yielding hydrogen bonds with the water molecule, LIF, R2PI, and HB spectroscopy of MAB(H2O)1 only pi...

Laser induced fluorescence, dispersed emission and two-colour ionisation spectroscopy (including the ionisation energy threshold) are suggested as an appropriate set of experimental methods for drawing the ground and excited state vibrational spectra of large organic molecules in presence of solvated molecules and dimers. In this Letter, they have been applied to obtain the vibrational spectrum of methyl- p -aminobenzoate (MAB). Parallel ground state ab initio calculations have enabled the geometry to be determined and the vibrational modes to be accurately assigned. The comparison of the ground and the first electronic excited state vibrational band wavenumbers shows an excellent agreement except for the excited state bands observed at 52.2, 565.6 and 579.7 cm −1 .

The ultrafast dynamics of the imidazole chromophore has been tracked after electronic excitation in the 250-217 nm energy region, by time delayed ionization with 800 nm laser pulses. The time-dependent signals collected at the imidazole(+) mass channel show the signature of femtosecond dynamics, originating on the πσ*- and ππ*-type states located in the explored energy region. The fitting of the transients, which due to the appearance of nonresonant coherent adiabatic excitation requires a quantum treatment based in the Bloch equations, yields two lifetimes of 18 ± 4 and 19 ± 4 fs. The first is associated with the πσ* ← ππ* internal conversion, while the second reflects the loss of ionization cross-section as the system evolves along the dissociative πσ* surface. This study provides a comprehensive picture of the photophysics of the molecule that agrees with previous experimental and theoretical findings.

The evolution of the isolated pyrrole molecule has been followed after excitation in the 265–217 nm range by using femtosecond time delayed ionization. The transients collected in the whole excitation range show the vanishing of the ionization signal in the femtosecond time scale, caused by the relaxation along a πσ* type state (3s a1←π 1a2), which is the lowest excited electronic state of the molecule. This surface is dissociative along the NH bond, yielding a 15 ± 3 fs lifetime that reflects the loss of the ionization cross-section induced by the ultrafast wavepacket motion. Although a weak πσ* absorption is detected, the state is mainly reached through internal conversion of the higher bright ππ* transitions, which occurs with a 19 ± 3 fs lifetime. In addition to its resonant excitation, the intense ππ* absorption extending in the 220–190 nm interval is also out-of-resonance populated at energies far to the red from its absorption onset. This coherent adiabatic excitation of the ππ* transition should follow the excitation pulse (coherent population return effect), but instead the system relaxes toward the lower πσ* surface through a conical intersection during the interaction time, leading to the population of πσ* state at wavelengths as long as 265 nm. According to the observed behavior, the time evolution of the system in the full excitation range studied is modeled by a coherent treatment that provides key insights on the photophysical properties of the molecule., This study was funded by Spanish MICINN (Grant No. CTQ2010-17749) and Consolider Program “Science and Applications of Ultrafast Ultraintense Lasers” (Grant No. CSD2007-00013), and by the Basque Government through the “Ayudas para apoyar las actividades de grupos de investigación del sistema universitario vasco” program. The experiments and theoretical calculations were carried out at the SGIker laser facility, and IZO-SGI of the UPV/EHU, respectively.

The ultrafast relaxation of jet-cooled aniline was followed by time-resolved ionization, after excitation in the 294-234 interval. The studied range of energy covers the absorption of the two bright ππ∗ excitations, S(1) and S(3), and the almost dark S(2) (πσ∗) state. The employed probe wavelengths permit to identify different ultrafast time constants related with the coupling of the involved electronic surfaces. A τ(1) = 165 ± 30 fs lifetime is attributed to dynamics along the S(2) (πσ∗) repulsive surface. Other relaxation channels as the S(1)→S(0) and S(3)→S(1) internal conversion are also identified and characterized. The work provides a general view of the photophysics of aniline, particularly regarding the role of the πσ∗ state. This state appears as minor dissipation process due to the ineffective coupling with the bright S(1) and S(3) states, being the S(1)→S(0) internal conversion the main non-radiative process in the full studied energy range. Additionally, the influence of the off-resonance adiabatic excitation of higher energy electronic states, particularly S(3), is also observed and discussed.

We report on the influence of coherent phenomena on femtosecond pump-probe experiments in molecular systems. The signature of Coherent Population Return (CPR) has been observed, and satisfactorily simulated, by following the dynamics of the on and off resonance excitation of the S(0)-S(1) transition of aniline. While for the on resonance experiments the system dynamics can be described in terms of the simple incoherent rate equations, for the off resonance experiments a more detailed analysis based on the time-dependent Schrödinger equation that takes into account coherent effects is needed. This fact points out the necessity of considering coherent effects during and after the interaction process, even in systems where ordinarily they have been neglected, for a rigorous description of laser mater interaction.

The conformational isomerization dynamics of N-acetyl tryptophan methyl amide (NATMA) and N-acetyl tryptophan amide (NATA) have been studied using the methods of IR-UV hole-filling spectroscopy (HFS) and IR-induced population transfer spectroscopy (IR-PTS), which were developed for this purpose. Single conformations of these molecules were selectively excited in well-defined NH stretch fundamentals. This excess energy was used to drive conformational isomerization. By carrying out the infrared excitation early in a supersonic expansion, the excited molecules were recooled into their zero-point levels, partially refilling the hole created in the ground state population of one of the conformers, and creating gains in population in other conformers. These changes in population were detected using laser-induced fluorescence downstream in the expansion. In HFS, the IR wavelength is fixed and the UV laser tuned in order to determine where the population went following selective infrared excitation. In IR-PTS, the UV is fixed to monitor the population of a given conformation, and the IR is tuned to record the IR-induced changes in the population of the monitored conformer. Besides demonstrating the capability of the experiment to change the downstream conformational population distribution, the IR-PTS scans were used to extract two quantitative results: (i) The fractional populations of the conformers in the absence of the infrared, and (ii) the isomerization quantum yields for each of the six unique amide NH stretch fundamentals (three conformers each with two amide groups). The method for obtaining quantum yields is described in detail. In both NATMA and NATA, the quantum yields show modest conformational specificity, but only a hint of vibrational mode specificity. The prospects for the hole-filling technique for providing insight into energy flow in large molecules are discussed, leaving a more detailed theoretical modeling to the adjoining paper [Evans et al. J. Chem. Phys. 120, 148 (2004)].

The dynamics of conformational isomerization are explored in a methyl-capped dipeptide, N -acetyl-tryptophan methyl amide (NATMA), using infrared-ultraviolet (IR-UV) hole-filling and IR-induced population transfer spectroscopies. IR radiation selectively excites individual NH stretch vibrational fundamentals of single conformations of the molecule in the early portions of a gas-phase expansion, and then this excited population is collisionally recooled into its conformational minima for subsequent conformation-specific detection. Efficient isomerization is induced by the IR excitation that redistributes population between the same conformations that have population in the absence of IR excitation. The quantum yields for transfer of the population into the various conformational minima depend uniquely on which conformation is excited and on which NH stretch vibration is excited within a given conformation.

Mass-resolved IR spectra of cyclohexanol-water clusters and cyclohexanol dimer in supersonic expansions are presented for the first time. A combination of ns and fs IR lasers made possible recording such spectra without inclusion of a chromophore or a messenger atom. Furthermore, employment of the recently developed IR(3) technique [I. León, R. Montero, F. Castaño, A. Longarte, and J. A. Fernández, J. Phys. Chem. A 116, 6798 (2012)] allowed us to discriminate between the contribution of different species to the IR spectrum. Comparison of the experimental spectra with the predictions at the M06-2X/6-311++G(d,p) calculation level confirmed the assignment of the spectrum of cyclohexanol·(H2O)1 to a structure in which water is accepting a proton from cyclohexanol's OH group, and those of cyclohexanol·(H2O)(2,3) to structures with cyclic hydrogen bond networks. A comparative analysis of the results obtained with those reported on other aromatic alcohols is also offered.

The ultrafast dynamics of the lowest optically accessible Rydberg states of molecular oxygen (O2) has been studied by time resolved transient ionization. The process was triggered by the absorption of two pump photons in the 304 nm-220 nm range which corresponds to an energy range of 8.2 eV-11.3 eV, and probed by ionization with photons at 800 nm. From the analysis of the experimental data different time constants ranging from a few femtoseconds to hundreds of picoseconds were found. The identification of the states responsible for the measured lifetimes revealed important facts about the dynamics of the Rydberg states in this energy range, underlying the importance of the coupling between Rydberg and valence states in the relaxation mechanisms of the molecule.

The ultrafast relaxation of 1-iodonaphthalene, with particular attention to the dissociation channels, has been studied by time-resolved femtosecond pump-probe mass spectrometry following excitation at 267 and 317 nm. The measured transients for the parent ion and the isobaric fragments, iodine and naphthyl radical, show complex decay profiles with up to four lifetimes in the femto-picosecond time scales. The transients are interpreted as the result of parallel relaxation of the simultaneously excited n sigma* and pi pi* states of the molecule. While the former leads to dissociation in about 400 fs, the latter converts to lower energy pi pi* singlet states at an ultrafast rate (24 fs) followed by intersystem crossing to nearby pi pi* triplet states.

Guaiacol (2-methoxyphenol) and eugenol (4-allyl-2-methoxyphenol) molecules are biologically active phenol derivatives with an intramolecular -OH...OCH3 hydrogen bond (H bond). Pulsed supersonic expansions of mixtures of either of the two molecules with He yield weakly bound homodimers as well as other higher-order complexes. A number of complementary and powerful laser spectroscopic techniques, including UV-UV and IR-UV double resonances, have been employed to interrogate the species formed in the expansion in order to get information on their structures and spectroscopic properties. The interpretation of the spectra of eugenol dimer is complex and required a previous investigation on a similar but simpler molecule both to gain insight into the possible structures and support the conclusions. Guaiacol (2-methoxyphenol) has been used for that purpose. The combination of the broad laser study combined with ab initio calculations at the Becke 3 Lee-Yang-Parr/6-31+Gd level has provided the isomer structures, the potential-energy wells, and shed light on the inter- and intramolecular interactions involved. Guaiacol homodimer has been shown to have a single isomer whereas eugenol dimer has at least two. The comparison between the computed geometries of the dimers, their respective energies, and the vibrational normal modes permits the identification of the spectra.

Eugenol (4-Allyl-2-methoxyphenol), a phenol-derivative with an intramolecular -OH ...OCH(3) hydrogen bond (H bond), has been studied in a supersonic expansion using a number of complementary laser spectroscopic techniques. The mass-resolved excitation spectrum of eugenol and its water complexes are reported for the first time. The most intense set of bands on the resonantly enhanced multiphoton ionization (REMPI) spectrum of eugenol originate in a conformer whose S(1)--S(0) transition is at 35 202 cm(-1) and the ionization threshold at (I(0)--S(0)) 62 544+/-150 cm(-1) (7.755+/-0.019 eV). In addition, two low intensity features redshifted with respect to the 0(0) (0) transition have been identified as due to a second, less stable conformer. Ab initio calculations show that the potential energy landscape depicts at least three minima associated with one folded and two extended conformers, one of which is the most stable. Clusters of eugenol/water were prepared in a supersonic expansion by seeding eugenol and water in noble gas He and examined by two-color REMPI (R2PI) and IR-UV double resonance spectroscopies. Only one single isomer was observed for both 1:1 and 1:2 complexes, in contrast with the several stable conformers provided by the computations. The dissociation energies of the 1:1 and 1:2 complexes have been determined by the fragmentation threshold method and the results compared with those from ab initio calculations conducted at the B3LYP and MP2 levels with a variety of basis sets.

The hydride stretch infrared spectra of indole, indole-H2O, 3-methyl indole, 3-methyl indole-H2O, the main conformer of tryptamine (TRA), two conformers of N-acetyl tryptophan amide (NATA), and three conformers of N-acetyl tryptophan methyl amide (NATMA), have been recorded in the electronically excited singlet states using excited-state fluorescence-dip infrared spectroscopy. NATA and NATMA are methyl-capped dipeptides of tryptophan that have conformational flexibility and exhibit sensitivity in their electronic spectra to the conformation of the dipeptide backbone. In the indole monomer, the indole NH stretch fundamental at the S1 origin is shifted from its ground-state value (3525 cm−1) to 3478 cm−1. The corresponding band in the indole-H2O complex appears at 3387 cm−1, shifted by a similar amount from its ground-state position (3436 cm−1). Higher vibronic levels within 1500 cm−1 of the S1 origin, which have been identified previously [B. J. Fender et al., Chem. Phys. Lett. 239, 31 (1995)] as being 1Lb...

Methyl-p-aminobenzoate(NH3)1 complex, henceforth MAB(NH3)1, prepared in a pulsed supersonic expansion, has been examined by laser mass-selective spectroscopies and density functional theory calculations, aiming to ascertain its isomer number, structures, identification, ionization energies, and vibrational assignments. Resonance enhanced multiphoton ionization and hole burning spectra of the species in supersonic beams show two 000 transitions redshifted by −715 and −709 cm−1 from that of bare MAB band origin and are plausibly associated with two different isomers, whereas ab initio calculations indicate the likely existence of five stable isomer structures. Identification of the experimental isomer spectra with the calculated structures is reported and, in particular, several isomer vibrational bands are identified by contrast with the calculated modes. Properties and features of the MAB(NH3)1 are compared with those of the MAB/water complexes.

A combined computational and experimental study of the methyl-p-aminobenzoate(H2O)n, (n=2,3,4) complexes [MAB(H2O)n] is reported. Complexes potential energy surfaces were explored by ab initio density functional theory (DFT) methods, at the B3LYP/6-31G level, and the stable isomer structures and vibrational modes further computed at the B3LYP/6-31+G* level. A set of self-contained experimental techniques, including laser induced fluorescence (LIF), resonance enhanced multiphoton ionization mass-resolved spectroscopy (REMPI), two-color resonance enhanced multiphoton ionization mass-resolved spectroscopy (R2PI), “hole burning” spectroscopy (HB), and two-color ionization thresholds were used to study the spectra and other physical features of the complexes. Of the three title complexes only MAB(H2O)4 has been observed with our experimental methods, while the MAB(H2O)3 was formed by evaporation and MAB(H2O)2 was not detected at all. It has been shown that the observed MAB(H2O)4 complex has only one isomer wit...