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We examine the properties of oblique coordinates. The coordinates, introduced by Zúñiga et al. [J. Phys. B: At., Mol. Opt. Phys. 52, 055101, (2019)], reduce vibrational mode-mixing and enhance the quality of vibrational assignments in quantum mechanical investigations of two-dimensional model Hamiltonians. Oblique coordinates are obtained by making non-orthogonal rotations of the original coordinates that convert the matrix representation of the quadratic Hamiltonian operator into a block-diagonal matrix where the blocks are distinguished by the total quanta of vibrational excitation. Using techniques for the polar decomposition of matrices, we present a scheme for finding these coordinates for systems of arbitrary dimensions. Several molecular examples are presented that highlight the advantages of these coordinates., (© 2023 Author(s). Published under an exclusive license by AIP Publishing.)

The vibrational signatures and ultrafast dynamics of the intramolecular H-bond in a series of β-diketones are investigated with 2D IR spectroscopy and computational modeling. The chosen β-diketones exhibit a range of H atom donor-acceptor distances and asymmetry along the H atom transfer coordinate that tunes the intramolecular H-bond strength. The species with the strongest H-bonds are calculated to have very soft H atom potentials, resulting in highly red-shifted OH stretch fundamental frequencies and dislocation of the H atom upon vibrational excitation. These soft potentials lead to significant coupling to the other normal mode coordinates and give rise to the very broad vibrational signatures observed experimentally. The 2D IR spectra in both the OH and OD stretch regions of the light and deuterated isotopologues reveal broadened and long-lived ground-state bleach signatures of the vibrationally hot molecules. Polarization-sensitive transient absorption measurements in the OH and OD stretch regions reveal notable isotopic differences in orientational dynamics. Orientational relaxation was measured to occur on ∼600 fs and ∼2 ps time scales for the light and deuterated isotopologues, respectively. The orientational dynamics are interpreted in terms of activated H/D atom transfer events driven by collective intramolecular structural rearrangements.

UV photofragment spectroscopy and IR-UV double resonance methods are used to determine the structure and spectroscopic responses of a three-dimensional [2.2.2]-benzocryptand cage to the incorporation of a single K + or Ba 2+ imbedded inside it (labeled as K + -BzCrypt, Ba 2+ -BzCrypt). We studied the isolated ion-cryptand complex under cryo-cooled conditions, brought into the gas phase by nano-electrospray ionization. Incorporation of a phenyl ring in place of the central ethyl group in one of the three N-CH 2 -CH 2 -O-CH 2 -CH 2 -O-CH 2 -CH 2 -N chains provides a UV chromophore whose S 0 -S 1 transition we probe. K + -BzCrypt and Ba 2+ -BzCrypt have their S 0 -S 1 origin transitions at 35,925 and 36,446 cm -1 , respectively, blue-shifted by 174 and 695 cm -1 from that of 1,2-dimethoxybenzene. These origins are used to excite a single conformation of each complex selectively and record their IR spectra using IR-UV dip spectroscopy. The alkyl CH stretch region (2800-3000 cm -1 ) is surprisingly sensitive to the presence and nature of the encapsulated ion. We carried out an exhaustive conformational search of cage conformations for K + -BzCrypt and Ba 2+ -BzCrypt, identifying two conformations (A and B) that lie below all others in energy. We extend our local mode anharmonic model of the CH stretch region to these strongly bound ion-cage complexes to predict conformation-specific alkyl CH stretch spectra, obtaining quantitative agreement with experiment for conformer A, the gas-phase global minimum. The large electrostatic effect of the charge on the O- and N-lone pairs affects the local mode frequencies of the CH 2 groups adjacent to these atoms. The localized CH 2 scissors modes are pushed up in frequency by the adjacent O/N-atoms so that their overtones have little effect on the alkyl CH stretch region. However, the localized CH 2 wags are nearly degenerate and strongly coupled to one another, producing an array of delocalized wag normal modes, whose highest frequency members reach up above 1400 cm -1 . As such, their overtones mix significantly with the CH stretch modes, most notably involving the CH 2 symmetric stretch fundamentals of the central ethyl groups in the all-alkyl chains and the CH stretches adjacent to the N-atoms and antiperiplanar to the nitrogen lone pair.

High-resolution vibrational spectra of C-H, O-H, and N-H stretches depend on both molecular conformation and environment as well as provide a window into the frequencies of many other vibrational degrees of freedom as a result of mode mixing. We review current theoretical strategies that are being deployed to both aid and guide the analysis of the data that are encoded in these spectra. The goal is to enhance the power of vibrational spectroscopy as a tool for probing conformational preferences, hydrogen bonding effects away from equilibrium, and energy flow pathways. Recent years have seen an explosion of new methods and strategies for solving the nuclear Schrödinger equation. Rather than attempt a comprehensive review, this work highlights specific molecular systems that we have chosen as representing bonding motifs that are important to chemistry and biology. We focus on the choices theoretical chemists make regarding the level of electronic structure theory, the representation of the potential energy surface, the selection of coordinates, preferences in basis sets, and methods of solution.

Phenol-benzimidazole and phenol-pyridine proton-coupled electron transfer (PCET) dyad systems are computationally investigated to resolve the origins of the asymmetrically broadened H-bonded OH stretch transitions that have been previously reported using cryogenic ion vibrational spectroscopy in the ground electronic state. Two-dimensional (2D) potentials describing the strongly shared H atom are predicted to be very shallow along the H atom transfer coordinate, enabling dislocation of the H atom between the donor and acceptor groups upon excitation of the OH vibrational modes. These soft H atom potentials result in strong coupling between the OH modes, which exhibit significant bend-stretch mixing, and a large number of normal mode coordinates. Vibrational spectra are calculated using a Hamiltonian that linearly and quadratically couples the H atom potentials to over two dozen of the most strongly coupled normal modes treated at the harmonic level. The calculated vibrational spectra qualitatively reproduce the asymmetric shape and breadth of the experimentally observed bands in the 2300-3000 cm -1 range. Interestingly, these transitions fall well above the predicted OH stretch fundamentals, which are computed to be surprisingly red-shifted (<2000 cm -1 ). Time-dependent calculations predict rapid (<100 fs) relaxation of the excited OH modes and instant response from the lower-frequency normal modes, corroborating the strong coupling predicted by the model Hamiltonian. The results highlight a unique broadening mechanism and complicated anharmonic effects present within these biologically relevant PCET model systems.

We report and interpret recently recorded high-resolution infrared spectra for the fundamentals of the CH 2 scissors and CH stretches of gas phase cyclopentane at -26.1 and -50 °C, respectively. We extend previous theoretical studies of this molecule, which is known to undergo barrierless pseudorotation due to ring puckering, by constructing local mode Hamiltonians of the stretching and scissor vibrations for which the frequencies, couplings, and linear dipoles are calculated as functions of the pseudorotation angle using B3LYP/6-311++(d,p) and MP2/cc-pVTZ levels of theory. Symmetrization (D 5h ) of the vibrational basis sets leads to simple vibration/pseudorotation Hamiltonians whose solutions lead to good agreement with the experiment at medium resolution, but which miss interesting line fractionation when compared to the high-resolution spectra. In contrast to the scissor motion, pseudorotation leads to significant state mixing of the CH stretches, which themselves are Fermi coupled to the scissor overtones.

D-Proline ( D Pro, D P) is widely utilized to form β-hairpin loops in engineered peptides that would otherwise be unstructured, most often as part of a D PG sub-unit that forms a β-turn. To observe whether D PG facilitated this effect in short protonated peptides, conformation specific IR-UV double resonance photofragment spectra of the cold (∼10 K) protonated D P and L P diastereomers of the pentapeptide YAPGA was carried out in the hydride stretch (2800-3700 cm -1 ) and amide I/II (1400-1800 cm -1 ) regions. A model localized Hamiltonian was developed to better describe the 1600-1800 cm -1 region commonly associated with the amide I vibrations. The CO stretch fundamentals experience extensive mixing with the N-H bending fundamentals of the NH 3 + group in these protonated peptides. The model Hamiltonian accounts for experiment in quantitative detail. In the D P diastereomer, all the population is funneled into a single conformer which presented as a type II β-turn with A and D P in the i + 1 and i + 2 positions, respectively. This structure was not the anticipated type II' β-turn across D PG that we had hypothesized based on solution-phase propensities. Analysis of the conformational energy landscape shows that both steric and charge-induced effects play a role in the preferred formation of the type II β-turn. In contrast, the L P isomer forms three conformations with very different structures, none of which were type II/II' β-turns, confirming that L PG is not a β-turn former. Finally, single-conformation spectroscopy was also carried out on the extended peptide [YAA D PGAAA + H] + to determine whether moving the protonated N-terminus further from D PG would lead to β-hairpin formation. Despite funneling its entire population into a single peptide backbone structure, the assigned structure is not a β-hairpin, but a concatenated type II/type II' double β-turn that displaces the peptide backbone laterally by about 7.5 Å, but leaves the backbone oriented in its original direction.

The NH stretch region of the IR spectrum of methyl anthranilate is modeled in the S 1 state to understand the connection between the absence of this fundamental in the fluorescence-dip infrared spectra of Blodgett et al. [ Phys. Chem. Chem. Phys. 2020 , 22 , 14077] and its relevance to the H atom dislocation that occurs upon electronic excitation. A set of coordinates are chosen that highlight the role of certain low-frequency modes. A Hamiltonian is developed in which a large-amplitude two-dimensional surface describing the H-bonded H atom is linearly and quadratically coupled to the remaining degrees of freedom which are treated at the harmonic level. The surface is calculated within the time-dependent density functional theory framework by using the B3LYP/6-311++(d, p) level of theory with dispersion. Our spectral results show that indirect couplings lead to massive intensity sharing over hundreds of wavenumbers. This sharing is predicted to be dramatically reduced upon deuteration. The spectral broadening mechanism is found to involve off-resonant doorway states that are themselves strongly coupled to states nearly degenerate with the NH stretch fundamental and represents a complementary mechanism to previous explanations based on Fermi resonance or the presence of Franck-Condon like combination bands with low-frequency motions. Consistent with the spectra predictions, time-dependent calculations show that if the NH stretch fundamental were excited with an ultrafast laser, it would decay within 40 fs. The competition between H atom dislocation and vibrational relaxation is discussed.

Intramolecular energy flow (also known as intramolecular vibrational redistribution or IVR) is often assumed in Rice-Ramsperger-Kassel-Marcus, transition state, collisional energy transfer, and other rate calculations not to be an impediment to reaction. In contrast, experimental spectroscopy, computational results, and models based on Anderson localization have shown that ergodicity is achieved rather slowly during molecular energy flow. The statistical assumption in rate theories might easily fail due to quantum localization. Here, we develop a simple model for the interplay of IVR and energy transfer and simulate the model with near-exact quantum dynamics for a 10-degree of freedom system composed of two five-mode molecular fragments. The calculations are facilitated by applying the van Vleck transformation to local random matrix models of the vibrational Hamiltonian. We find that there is a rather sharp "phase transition" as a function of molecular anharmonicity "a" between a region of facile energy transfer and a region limited by IVR and incomplete accessibility of the state space (classically, the phase space). The very narrow transition range of the order parameter a happens to lie right in the middle of the range expected for molecular torsion, bending, and stretching vibrations, thus demonstrating that reactive energy transfer dynamics several k B T above the thermal energy occurs not far from the localization boundary, with implications for controllability of reactions.

Revisiting recently published Raman jet spectra of monomeric formic acid with accurate high order perturbative calculations based on two explicitly correlated coupled-cluster quality potential energy surfaces from the literature, we assign and add 11 new vibrational band centers to the trans-HCOOH database and 53 for its three deuterated isotopologs. Profiting from the synergy between accurate calculations and symmetry information from depolarized Raman spectra, we reassign eight literature IR bands up to 4000 cm -1 . Experimental detection of highly excited torsional states (ν 9 ) of trans-HCOOH, such as 4ν 9 and ν 6 + 2ν 9 , reveals substantial involvement of the C-O stretch ν 6 into the O-H bend/torsion resonance ν 5 /2ν 9 , which is part of a larger resonance polyad. Depolarization and isotopic C-D substitution experiments further elucidate the nature of Raman peaks in the vicinity of the O-H stretching fundamental (ν 1 ), which seem to be members of a large set of interacting states that can be identified and described with a polyad quantum number and that gain intensity via resonance mixing with ν 1 .

Laser-induced fluorescence (LIF) excitation, dispersed fluorescence (DFL), UV-UV-hole burning, and UV-depletion spectra have been collected on methyl anthranilate (MA, methyl 2-aminobenzoate) and its water-containing complex (MA-H 2 O), under jet-cooled conditions in the gas phase. As a close structural analog of a sunscreen agent, MA has a strong absorption due to the S 0 -S 1 transition that begins in the UV-A region, with the electronic origin at 28 852 cm -1 (346.6 nm). Unlike most sunscreens that have fast non-radiative pathways back to the ground state, MA fluoresces efficiently, with an excited state lifetime of 27 ns. Relative to methyl benzoate, inter-system crossing to the triplet manifold is shut off in MA by the strong intramolecular NHO[double bond, length as m-dash]C H-bond, which shifts the 3 nπ* state well above the 1 ππ* S 1 state. Single vibronic level DFL spectra are used to obtain a near-complete assignment of the vibronic structure in the excited state. Much of the vibrational structure in the excitation spectrum is Franck-Condon activity due to three in-plane vibrations that modulate the distance between the NH 2 and CO 2 Me groups, ν 33 (421 cm -1 ), ν 34 (366 cm -1 ), and ν 36 (179 cm -1 ). Based on the close correspondence between experiment and theory at the TD-DFT B3LYP-D3BJ/def2TZVP level of theory, the major structural changes associated with electronic excitation are evaluated, leading to the conclusion that the major motion is a reorientation and constriction of the 6-membered H-bonded ring closed by the intramolecular NHO[double bond, length as m-dash]C H-bond. This leads to a shortening of the NHO[double bond, length as m-dash]C H-bond distance from 1.926 Å to 1.723 Å, equivalent to about a 25% reduction in the HO distance compared to full H-atom transfer. As a result, the excited state process near the S 1 origin is a hydrogen atom dislocation that is brought about primarily by heavy atom motion, since the shortened H-bond distance results from extensive heavy-atom motion, with only a 0.03 Å increase in the NH bond length relative to its ground state value.

In this perspective, we review the challenges of calculating spectra of high-frequency XH vibrations (where X = C, N, or O) of molecules and small clusters. These modes are often coupled to nearly degenerate overtone and combination bands, greatly complicating the interpretation of the spectra. When molecules or clusters contain multiple XH groups, assigning spectra is difficult, especially when multiple conformers are present. We consider approaches appropriate for addressing these difficulties, focusing on systems with more than 15 atoms. At this size, the densities of states of these fundamentals are sufficiently high that it is not possible to calculate eigenstate-resolved spectra. Nonetheless, combining perturbation theory, empirical scalings of vibrational frequencies, and variational treatments of reduced dimensional Hamiltonians, one can identify and model the vibrational coupling pathways that influence observed spectral features. We describe how these methods have evolved through time as electronic structure methods and computational resources have advanced.

An ultraviolet-infrared (UV-IR) double-resonance method for recording conformation-specific excited-state infrared spectra is described. The method takes advantage of an increase in fluorescence signal in phenylalkanes produced by infrared excitation of the S 1 origin levels of different conformational isomers. The shorter lifetimes of these IR-excited molecules, combined with their red-shifted emission, provides a way to discriminate the fluorescence due to the infrared-excited molecules from the S 1 origin fluorescence, resulting in spectra with high signal-to-noise ratios. Spectra for a series of phenylalkanes and a capped phenylalanine derivative (Ac-Phe-NHMe) demonstrate the potential of the method. The excited-state spectrum in the alkyl CH stretch region of ethylbenzene is well-fit by an anharmonic model developed for the ground electronic state, which explicitly takes into account stretch-bend Fermi resonance.

The investigation of partially deuterated methoxy radicals is important because the symmetry lowering from C 3v to C s provides new insights into the couplings between rovibronic states via Jahn-Teller and spin-orbit interactions. The vibrational spectrum of the partially deuterated methoxy radical CH 2 DO in a matrix of p-H 2 has been recorded. This species was prepared by irradiating a p-H 2 matrix containing deuterated d 1 -nitritomethane (CH 2 DONO) at 3.3 K with laser light at 355 nm. The identification of the radical is based on the photochemical behavior of the precursor and comparison of observed vibrational wavenumbers and infrared (IR) intensities with those predicted from a refined quartic, curvilinear, internal coordinate force field calculated with the coupled-cluster singles and doubles with perturbative triples/cc-pVTZ method. CH 2 DO reacts with H 2 with a rate coefficient (3.5 ± 1.0) × 10 -3 s -1 . Predominantly c-CHDOH and a negligibly small amount of t-CHDOH were produced. This stereoselectivity results from the reaction H + C s -CH 2 DOH, which was demonstrated by an additional experiment on irradiation of a CH 2 DOH/Cl 2 /p-H 2 matrix with ultraviolet and IR light to induce the H + CH 2 DOH reaction; only c-CHDOH was observed from this experiment. Even though the energies of transition states and products for the formation of c-CHDOH and t-CHDOH differ by only ∼10 cm -1 , the selective formation of c-CHDOH can be explained by tunneling of the hydrogen atom via an optimal tunneling path. Similarly, the vibronic spectrum for the partially deuterated specie d 2 -methoxy radical (CHD 2 O) was obtained upon irradiation of d 2 -nitritomethane (CHD 2 ONO) at 355 nm. Lines associated with the fundamental vibrational modes were observed and assigned; line positions agree with theoretically predicted vibrational wavenumbers. CHD 2 O reacts with H 2 with a rate coefficient (6.0 ± 1.4) × 10 -3 s -1 ; CD 2 OH was produced as a major product because the barrier for the formation of CHDOH from H + CHD 2 OH is greater by ∼400 cm -1 . Rate coefficients of the decays of CH 3 O, CH 2 DO, CHD 2 O, and CD 3 O and their corresponding potential energy surfaces are compared.

The assignment of lines in vibrational spectra in strongly mixing systems is considered. Several low lying vibrational states of the ground electronic X∼ 2 E state of the CH 3 O and CD 3 O radicals are assigned. Jahn-Teller, spin-orbit, and Fermi couplings mix the normal mode states. The mixing complicates the assignment of the infrared spectra using a zero-order normal mode representation. Alternative zero-order representations, which include specific Jahn-Teller couplings, are explored. These representations allow for definitive assignments. In many instances it is possible to plot the wavefunctions on which the assignments are based. The plots, which are shown in the adiabatic representation, allow one to visualize the effects of various higher order couplings. The plots also enable one to visualize the conical seam and its effect on the wavefunctions. The first and the second order Jahn-Teller couplings in the rocking motion dominate the spectral features in CH 3 O, while first order and modulated first order couplings dominate the spectral features in CD 3 O. The methods described here are general and can be applied to other Jahn-Teller systems.

The n-propyl and i-propyl radicals were generated in the gas phase via pyrolysis of n-butyl nitrite [CH 3 (CH 2 ) 3 ONO] and i-butyl nitrite [(CH 3 ) 2 CHCH 2 ONO], respectively. Nascent radicals were promptly solvated by a beam of He nanodroplets, and the infrared spectra of the radicals were recorded in the CH stretching region. Several previously unreported bands are observed between 2800 and 3150 cm -1 . The CH stretching modes observed above 3000 cm -1 are in excellent agreement with CCSD(T) anharmonic frequencies computed using second-order vibrational perturbation theory. However, between 2800 and 3000 cm -1 , the spectra of n- and i-propyl radicals become congested and difficult to assign due to the presence of multiple anharmonic resonance polyads. To model the spectrally congested region, Fermi and Darling-Dennison resonances are treated explicitly using "dressed" Hamiltonians and CCSD(T) quartic force fields in the normal mode representation, and the agreement with experiment is less than satisfactory. Computations employing local mode effective Hamiltonians reveal the origin of the spectral congestion to be strong coupling between the high frequency CH stretching modes and the lower frequency CH n bending/scissoring motions. The most significant coupling is between stretches and bends localized on the same CH 2 /CH 3 group. Spectral simulations using the local mode approach are in excellent agreement with experiment.

An important initial step in the combustion of gasoline and diesel fuels is the abstraction of hydrogen from alkylbenzenes to form resonance-stabilized alkyl benzyl radicals. This work uses, for the first time, double resonance spectroscopy methods to explore the conformation-specific vibronic and infrared spectroscopy of the α-ethylbenzyl (αEtBz) and α-propylbenzyl (αPrBz) radicals. Local mode Hamiltonian modeling enables assignment of the alkyl CH stretch IR spectra, accounting for Fermi resonance that complicates aliphatic alkyl CH stretch IR spectroscopy. The ground state conformational preferences of the ethyl and propyl chains are changed from those in the alkylbenzenes themselves, with global minima occurring for an in-plane orientation of the alkyl chain (trans) about its first dihedral angle (ϕ f123 , numbers are alkyl C atoms. C 1 is CH radical site). This in-plane structure is the only observed conformer for the α-EtBz radical, while two conformers, tt and tg' share this orientation at the first dihedral, but differ in the second (ϕ 1234 ) for the αPrBz radical. The in-plane orientation lowers the local site frequencies of the CH 2 group stretches immediately adjacent to the benzylic radical site by about 50 cm -1 relative to those in pure alkyl chains or alkylbenzenes. This effect of the radical site is localized on the first CH 2 group, with little effect on subsequent members of the alkyl chain. In the D 1 excited electronic state, an out-of-plane orientation is preferred for the alkyl chains, leading to torsional mode Franck-Condon activity in the D 0 -D 1 spectra that is both conformer-specific and diagnostic of the conformational change.

Conformation-specific UV-IR double resonance spectra are presented for ethyl, n-propyl, and n-butylbenzene. With the aid of a local mode Hamiltonian that includes the effects of stretch-scissor Fermi resonance, the spectra can be accurately modeled for specific conformers. These molecules allow for further development of a first principles method for calculating alkyl stretch spectra. Across all chain lengths, certain dihedral patterns impart particular spectral motifs at the quadratic level. However, the anharmonic contributions are consistent from molecule to molecule and conformer to conformer. This transferability of anharmonicities allows for the Hamiltonian to be constructed from only a harmonic frequency calculation, reducing the cost of the model. The phenyl ring alters the frequencies of the CH2 stretches by about 15 cm(-1) compared to their n-alkane counterparts in trans configurations. Conformational changes in the chain can lead to shifts in frequency of up to 30 cm(-1).

The CH stretch vibrations of M(+)[cyclohexane][Ar] (M = Li, Na, and K) cluster ions were theoretically modeled. Results were compared to the corresponding infrared photodissociation spectra of Patwari and Lisy [ J. Chem. Phys A 2007 , 111 , 7585 ]. The experimental spectra feature a substantial spread in CH stretch vibration frequencies due to the alkali metal cation binding to select hydrogens of cyclohexane. This spread was observed to increase with decreasing metal ion size. Exploring the potential energy landscape revealed the presence of three conformers whose energy minima lie within ∼1 kcal of each other. It was determined that in all conformers the metal ion interacts with three hydrogen atoms; these hydrogen atoms can be either equatorial or axial. The corresponding spectra for these conformers were obtained with a theoretical model Hamiltonian [ J. Chem. Phys. 2013 , 138 , 064308 ] that consists of local mode CH stretches bilinearly coupled to each other and Fermi coupled to lower frequency modes. Frequencies and coupling parameters were obtained from electronic structure calculations that were subsequently scaled on the basis of previous studies. Theoretical spectra of a single low energy conformer were found to match well with the experimental spectra. The relative frequency shifts with changing metal ion size were accurately modeled with parameters generated by using ωB97X-D/6-311++(2d,p) calculations.

Isomer-specific resonant ion-dip infrared spectra are presented for benzene-water (Bz-(H2O)n) clusters with two to seven water molecules. Local mode Hamiltonians based on scaled M06-2X/6-311++G(2d,p) density functional calculations are presented that accurately model the spectra across the entire OH stretch region (3000-3750 cm(-1)). The model Hamiltonians include the contribution from the water bend overtone and an empirical parameter for the local OH stretch-bend Fermi coupling. The inclusion of this coupling is necessary for accurate modeling of the infrared spectra of clusters with more than three water molecules. For the cyclic water clusters (n = 3-5), the benzene molecule perturbs the system in a characteristic way, distorting the cycle, splitting degeneracies, and turning on previously forbidden transitions. The local OH stretch site frequencies and H···OH hydrogen bond lengths follow a pattern based on the each water monomer's proximity to benzene. The patterns observed for these cyclic water clusters provide insight into benzene's effects on the three-dimensional hydrogen-bonded networks present in water hexamer and heptamer structures, which also have their spectra dramatically altered from their pure water counterparts.

The water hexamer and heptamer are the smallest sized water clusters that support three-dimensional hydrogen-bonded networks, with several competing structures that could be altered by interactions with a solute. Using infrared-ultraviolet double resonance spectroscopy, we record isomer-specific OH stretch infrared spectra of gas-phase benzene-(H2O)(6,7) clusters that demonstrate benzene's surprising role in reshaping (H2O)(6,7). The single observed isomer of benzene-(H2O)6 incorporates an inverted book structure rather than the cage or prism. The main conformer of benzene-(H2O)7 is an inserted-cubic structure in which benzene replaces one water molecule in the S4-symmetry cube of the water octamer, inserting itself into the water cluster by engaging as a π H-bond acceptor with one water and via C-H···O donor interactions with two others. The corresponding D(2d)-symmetry inserted-cube structure is not observed, consistent with the calculated energetic preference for the S4 over the D(2d) inserted cube. A reduced-dimension model that incorporates stretch-bend Fermi resonance accounts for the spectra in detail and sheds light on the hydrogen-bonding networks themselves and on the perturbations imposed on them by benzene.

Small symmetric molecules and low-dimensional model Hamiltonians are excellent systems for benchmarking theories to compute tunneling splittings. In this work, we investigate a three dimensional model Hamiltonian coupled to a harmonic bath that describes concerted proton transfer in the formic acid dimer. The three modes include the symmetric proton stretch, the symmetric dimer rock, and the dimer stretch. These modes provide a paradigm for the symmetric and anti-symmetric coupled tunneling pathways, these being recognized in the literature as two of the more important classes of coupling. The effects of selective vibrational excitation and coupling to a bath on the tunneling splittings are presented. The splittings for highly excited states are computed using a novel method that makes an adiabatic approximation to the Herring estimate. Results, which are in excellent agreement with the exact splittings, are compared with those obtained using the Makri-Miller approach. This latter method has been shown to provide quality results for tunneling splittings including highly excited vibrational states.

A theoretical model Hamiltonian [J. Chem. Phys. 2013, 138, 064308] for describing vibrational spectra associated with the CH stretch of CH2 groups is extended to molecules containing methyl and methoxy groups. Results are compared to the infrared (IR) spectroscopy of four molecules studied under supersonic expansion cooling in gas phase conditions. The molecules include 1,1-diphenylethane (DPE), 1,1-diphenylpropane (DPP), 2-methoxyphenol (guaiacol), and 1,3-dimethoxy-2-hydroxybenzene (syringol). Transforming the bending normal mode vibrations of CH3 groups to local scissor vibrations leads to model Hamiltonians which share many features present in our model Hamiltonian for the stretching vibrations of CH2 Fermi coupled to scissor modes. The central difference arises from the greater scissor-scissor coupling present in the CH3 case. Comparing anharmonic couplings between these modes and the stretch-bend Fermi coupling for a variety of systems, it is observed that the anharmonic couplings are robust; their values are similar for the four molecules studied as well as for ethane and methanol. Similar results are obtained with both density functional theory and coupled-cluster calculations. This robustness suggests a new parametrization of the model Hamiltonian that reduces the number of fitting parameters. In contrast, the harmonic contributions to the Hamiltonian vary substantially between the molecules leading to important changes in the spectra. The resulting Hamiltonian predicts most of the major spectral features considered in this study and provides insights into mode mixing and the consequences of the mixing on dynamical processes that follow ultrafast CH stretch excitation.

The infrared (IR) spectroscopy of the alkyl CH stretch region (2750-3000 cm(-1)) of a series of bicyclic hydrocarbons and free radicals has been studied under supersonic expansion cooling in the gas phase, and compared with a theoretical model that describes the local mode stretch-bend Fermi resonance interactions. The double resonance method of fluorescence-dip infrared (FDIR) spectroscopy was used on the stable molecules 1,2-dihydronaphthalene, 1,4-dihydronaphthalene, tetralin, indene, and indane using the S0-S1 origin transition as a monitor of transitions. Resonant ion-dip infrared (RIDIR) spectra were recorded for the trihydronaphthyl (THN) and inden-2-yl methyl (I2M) radicals. The previously developed model Hamiltonian (J. Chem. Phys. 2013, 138, 064308) incorporates cubic stretch-bend coupling with parameters obtained from density functional theory methods. Full dimensional calculations are compared to reduced dimensional Hamiltonian results in which anharmonic CH stretches and CH2 scissor modes are Fermi coupled. Excellent agreement between theoretical results is found. Scale factors of select terms in the reduced dimensional Hamiltonian, obtained by fitting the theoretical Hamiltonian predictions to the experimental spectra, are found to be similar to previous work. The resulting Hamiltonian predicts successfully all the major spectral features considered in this study. A simplified model is introduced in which the CH2 groups are decoupled. This model enables the assignment of many of the spectral features. The model results are extended to describe the CH stretch spectrum of the chair and twist-boat conformers of cyclohexane. The chair conformer is used to illustrate the shortcomings of the CH2 decoupling model.

The alkyl and aromatic CH stretch infrared spectra of inden-2-ylmethyl (I2M, C10H9) and trihydronaphthyl (THN, C10H11) radicals have been recorded under jet-cooled conditions in the ground (D0) and first electronically excited (D1) states using resonant ion-dip infrared (RIDIR) spectroscopy. Previously, the vibronic spectroscopy of a series of C10H9 and C10H11 hydronaphthyl radicals were investigated and their thermochemical properties were evaluated with isomer specificity [J. A. Sebree et al., J. Phys. Chem. A 11, 6255-6262 (2010)]. We show here that one of the m/z 129 spectral carriers characterized in that work was misidentified as 2-hydronaphthyl (2-HN) radical, appearing in a discharge of 1,2-dihydronaphthalene in close proximity to 1-hydronaphthyl radical. The D0-RIDIR spectrum in the alkyl CH stretch region positively identifies the m/z 129 isomer as I2M, whose two-color resonant two-photon ionization (2C-R2PI) spectrum was recently reported by Schmidt and co-workers [T. P. Troy et al., Chem. Sci. 2, 1755-1765 (2011)]. Here, we further characterize the I2M and THN radicals by recording their gas phase IR spectra in the alkyl and aromatic CH stretch regions, and explore the spectroscopic consequences of electronic excitation on the CH stretch absorptions. A local-mode CH stretch Hamiltonian incorporating cubic stretch-bend coupling between anharmonic CH stretches and CH2 scissor modes is utilized to describe their Fermi resonance interactions. Excellent agreement between the experimental and theoretical results facilitates the interpretation of the D0- and D1-state RIDIR spectra of I2M, revealing that upon excitation the alkyl CH stretches decrease in frequency by 70 cm(-1), while the allyl-like CH stretches experience a modest blueshift. In comparison, the photophysics of THN are strikingly different in that the IR transitions that possess vibrational motion along the CβH and CδH bonds are absent in the D1-RIDIR spectrum yet are predicted to be present from the theoretical model. Several hypotheses are considered to account for the perturbations to these vibrations.

A theoretical calculation of the laser-induced fluorescence excitation spectrum from X̃(2)E→Ã(2)A1 is carried out for CH3O and CD3O using a transition dipole moment surface expanded up to second order. The vibronic form of these operators is obtained using symmetry arguments. The Ã(2)A1 vibrational levels are calculated using Van Vleck perturbation theory, and the latter is used to adjust harmonic constants of the potential to match experimental fundamentals. The CH3O fit force field is tested on CD3O. For both molecules the transition energies are well reproduced, but there are systematic differences between experimental and theoretical intensities. The origins of these differences are discussed., (Copyright © 2013 Elsevier B.V. All rights reserved.)

Electronically exciting the C-I stretch in the molecule chloroiodomethane CH2ClI embedded in a matrix of argon at 12 K can lead to an isomer, iso-chloroiodomethane CH2Cl-I, that features a chlorine iodine bond. By temporally probing the isomer at two different frequencies of 435 nm and 485 nm, multiple timescales for isomerization and vibrational energy relaxation were inferred [T. J. Preston, et al., J. Chem. Phys. 135, 114503 (2011)]. This relaxation is studied theoretically using molecular dynamics by considering 2 and 3 dimensional models. Multiple decay rate constants of the same order of magnitude as the experiment are observed. These decay rate constants are interpreted within the context of the Landau-Teller theory. Sensitivity of the decay rate constants on the bath and system parameters shed more light into the mechanism of vibrational energy relaxation.

1,2-Diphenoxyethane (C6H5-O-CH2-CH2-O-C6H5, DPOE) is a flexible bichromophore in which the two phenyl rings are separated from one another by an -O-CH2-CH2-O- chain with five flexible dihedral angles about which hindered rotation can occur. As such, it is a phenyl capped analog of dimethoxyethane (DMOE), which has served as a model compound for development of force fields for polyethylene glycol (PEG). The ground state conformational energy landscape of DPOE is explored using a combination of single-conformation spectroscopy of the jet-cooled molecule and calculations of the conformational minima and transition states. In the experimental UV spectrum, ultraviolet hole-burning establishes the presence of just two conformations with significant population in the supersonic jet expansion. Fluorescence dip infrared (FDIR) spectroscopy is used to record infrared spectra of the two conformers in the alkyl CH stretch, CH bend, and CO stretch regions. When compared with harmonic vibrational frequency calculations, the two isomers are determined to be of C2h and C2 symmetry, and labeled ttt and tgt to denote the three central dihedrals as trans or gauche. Infrared population transfer spectroscopy is used to determine fractional abundances for the two conformers (f(ttt) = 0.53 ± 0.01; f(tgt) = 0.47 ± 0.01). Relaxed potential energy curves along the three nonequivalent dihedral angles are used to map out the shape of the potential energy landscape that leads to these preferences. The Fermi resonance in the alkyl CH stretch spectrum is successfully modeled using a recently developed methodology [Buchanan et al., J. Chem. Phys. 2013, 138, 064308] employing a reduced dimension Hamiltonian. The scissor overtones couple to the CH2 symmetric stretch and only indirectly to the asymmetric stretch through symmetric stretch/asymmetric stretch coupling. The presence of the oxygen atoms in the chain shifts the CH scissor overtones to higher frequencies than in pure alkyl chains, qualitatively changing the spectral consequences of the Fermi resonance, with the scissor overtones now appearing as the highest frequency bands in the spectrum. The spectra are contrasted with those in 1,2-diphenylethane, a close analog with a very different appearance to its CH stretch spectrum, in which the scissor overtones appear as the lowest frequency bands.

The spectroscopy of two flexible hydrocarbons, 1,2-diphenylethane (DPE) and 2,2,2-paracyclophane (TCP) is presented, and a predictive theoretical model for describing the alkyl CH stretch region of these hydrocarbons is developed. Ultraviolet hole-burning spectroscopy identified two isomers of DPE and a single conformation of TCP present in the supersonic jet expansion. Through the analysis of the ground state low-frequency vibronic spectroscopy obtained by dispersed fluorescence, conformational assignments were made for both DPE and TCP. The two isomers of DPE were found to retain the low energy structures of butane, being present in both the gauche and anti structures. TCP forms a C(2) symmetric structure, differing from the predicted lower energy C(3) conformation by the symmetry of the ethano bridges (-CH(2)CH(2)-) linking the phenyl substituents. Resonant ion-dip infrared spectroscopy is used to record single-conformation IR spectra of the two conformers of DPE and the single conformer of TCP in the alkyl CH stretch region and in the mid-IR that covers the CH bend fundamentals. A local mode Hamiltonian that incorporates cubic stretch-bend coupling is developed. Its parameters are obtained from density functional theory methods. Full dimensional calculations are compared to those that use reduced dimensional Hamiltonians in which anharmonic CH stretches and scissor modes are Fermi coupled. Excellent agreement is found. Scale factors of select terms in the reduced dimensional Hamiltonian are determined by fitting the theoretical Hamiltonian to the anti-DPE spectrum. The scaled Hamiltonian is then used to predict successfully structures for the remaining lower symmetry experimentally determined spectra in the alkyl CH stretch region.

The mixed quantum-classical surface hopping method is applied to the vibrational predissociation of methanol dimer, and the results are compared to more exact quantum calculations. Utilizing the vibrational SCF basis, the predissociation problem is cast into a curve crossing problem between dissociative and quasibound surfaces with different vibrational character. The varied features of the dissociative surfaces, arising from the large amplitude OH torsion, generate rich predissociation dynamics. The fewest switches surface hopping algorithm of Tully [J. Chem. Phys. 93, 1061 (1990)] is applied to both diabatic and adiabatic representations. The comparison affords new insight into the criterion for selecting the suitable representation. The adiabatic method's difficulty with low energy trajectories is highlighted. In the normal crossing case, the diabatic calculations yield good results, albeit showing its limitation in situations where tunneling is important. The quadratic scaling of the rates on coupling strength is confirmed. An interesting resonance behavior is identified and is dealt with using a simple decoherence scheme. For low lying dissociative surfaces that do not cross the quasibound surface, the diabatic method tends to overestimate the predissociation rate whereas the adiabatic method is qualitatively correct. Analysis reveals the major culprits involve Rabi-like oscillation, treatment of classically forbidden hops, and overcoherence. Improvements of the surface hopping results are achieved by adopting a few changes to the original surface hopping algorithms.

The J = 0 infrared spectrum of methoxy is theoretically calculated for the ground X̃(2)E state using a quartic potential energy force field, and the quadratic dipole moment expansion is calculated ab initio at the CCSD(T) level of theory and cc-pVTZ basis. Writing these expansions with vibronic operators whose symmetry properties are defined with respect to C(3v) rotation greatly simplifies these calculations. With minor adjustments to the force field, excellent agreement with experiment is found for both the transition energies of CH(3)O and those of CD(3)O. The role of Jahn-Teller and Fermi coupling is illustrated by scaling these terms by a parameter δ that varies from 0 to 1. Plotting the eigenvalues as a function of δ yields a correlation diagram connecting the harmonic eigenvalues to those of the fully coupled problem. The spectrum for CH(3)O is determined using a combination of Davidson and Lanczos iteration schemes. The spectral features are found to be dominated by Jahn-Teller effects, but direct Fermi coupling and indirect potential couplings have important roles. The origin of the complexities in the CH stretch region are discussed., (© 2012 American Chemical Society)

We present a general approach for modeling multidimensional infrared spectra based on a combination of phenomenological fitting and ab initio electronic structure calculations. The vibrational Hamiltonian is written in terms of bilinearly coupled Morse oscillators that represent local carbonyl stretches. This should be contrasted with the previous approach, where the anharmonic Hamiltonian was given in terms of normal-mode coordinates ( Baiz et al. J. Phys. Chem. A 2009 , 113 , 9617 ). The bilinearly coupled Morse oscillator Hamiltonian is parametrized such that the frequencies and couplings are consistent with experiment, and the anharmonicities are computed by density functional theory. The advantages of the local-mode versus normal-mode approaches are discussed, as well as the ability of different density functionals to provide accurate estimates of the model parameters. The applicability and usefulness of the new approach are demonstrated in the context of the recently measured multidimensional infrared spectra of dimanganese decacarbonyl. The shifts in local site frequencies, couplings, and anharmonicities due to hydrogen bonding to the individual carbonyls are explored. It is found that, even though the effect of hydrogen bonding is nonlocal, it is additive., (© 2011 American Chemical Society)

Nuclear magnetic resonance spectroscopy relies on using multiple excitation pulses to create multiple quantum coherences that provide great specificity for chemical measurements. Coherent multidimensional spectroscopy (CMDS) is the optical analogue of NMR. Current CMDS methods use three excitation pulses and phase matching to create zero, single, and double quantum coherences. In order to create higher order multiple quantum coherences, the number of interactions must be increased by raising the excitation intensities high enough to create Rabi frequencies that are comparable to the dephasing rates of vibrational coherences. The higher Rabi frequencies create multiple, odd-order coherence pathways. The coherence pathways that involve intermediate populations are partially coherent and are sensitive to population relaxation effects. Pathways that are fully coherent involve only coherences and measure the direct coupling between excited quantum states. The fully coherent pathways are related to the multiple quantum coherences created in multiple pulse NMR methods such as heteronuclear multiple quantum coherence (HMQC) spectroscopy with the important difference that HMQC NMR methods have a defined number of interactions and avoid dynamic Stark effects whereas the multiply enhanced odd-order wave-mixing pathways do not. The difference arises because CMDS methods use phase matching to define the interactions and at high intensities, multiple pathways obey the same phase matching conditions. The multiple pathways correspond to the pathways created by dynamic Stark effects. This paper uses rhodium dicarbonyl chelate (RDC) as a model to demonstrate the characteristics of multiply enhanced odd-order wave-mixing (MEOW) methods. Dynamic Stark effects excite vibrational ladders on the symmetric and asymmetric CO stretch modes and create a series of multiple quantum coherences and populations using partially and fully coherent pathways. Vibrational quantum states up to v = 6 are excited. A series of spectra provides different two-dimensional cross sections through the multidimensional parameter space involving two excitation frequencies, the frequency of the output coherence, and the excitation pulse time delays. The spectra allow the identification of 18 different overtone and combination band states. Comparison with a local mode model with two anharmonic Morse oscillators with interbond coupling shows excellent agreement.

Recent infrared pump-probe studies on alcohol oligomers in CCl(4) solution reveal that, following OH stretch excitation, ultrafast hydrogen bond (H-bond) breaking takes place on a time scale of 1 ps. To shed light on the mechanism of the H-bond breaking, we consider vibrational predissociation of the H-bonded methanol dimer. We construct a four-dimensional model for the dimer including the H-bond stretch, the donor OH stretch, the donor COH bend, and the OH rotation about the CO axis of the donor. Predissociation rates are calculated with Fermi's golden rule and close coupling approaches. Our results indicate that the predissociation leads to products with highly excited OH rotations. The predissociation rates strongly depend on the hydrogen bond strength. From our results, a simple nonadiabatic curve crossing picture for the predissociation process emerges, which provides a framework for future studies of solvent-assisted vibrational predissociation.

Studies of vibrational energy flow in various polar and nonpolar molecules that follows the ultrafast excitation of the CH and OH stretch fundamentals, modeled using semiclassical methods, are reviewed. Relaxation rates are calculated using Landau-Teller theory and a time-dependent method, both of which consider a quantum mechanical solute molecule coupled to a classical bath of solvent molecules. A wide range of decay rates are observed, ranging from 1 ps for neat methanol to 50 ps for neat bromoform. In order to understand the flow rates, it is argued that an understanding of the subtle mixing between the solute eigenstates is needed and that solute anharmonicities are critical to facilitating condensed phase vibrational relaxation. The solvent-assisted shifts of the solute vibrational energy levels are seen to play a critical role of enhancing or decreasing lifetimes.

We extend the reaction surface Hamiltonian model for double proton tunneling in formic acid dimer to include all in-plane modes, except the two CH stretch modes. Zero point corrections for the out-of-plane modes are also incorporated. Transition state and equilibrium normal mode representations for the description of the asymmetric modes are developed and compared. The results compare well with reduced dimensional calculations containing just symmetric in-plane modes due to a fortuitous cancellation of tunneling contributions of the out-of-plane and in-plane asymmetric modes. The effects of scaling the potential are examined as well as the effects of asymmetric vibrational excitation on tunneling splittings. Vibrational excitation of the asymmetric dimer rock, in contrast to the symmetric rock, is found to hinder tunneling. We find qualitative agreement with the experimental measurements of Ortlieb and Havenith [J. Phys. Chem. 111, 7355 (2007)] for the tunneling splitting of the ground state; the decrease in splitting upon vibrational excitation of CO stretch, however, is overestimated.

A model of double proton tunneling in formic acid dimer is developed using a reaction surface Hamiltonian. The surface includes the symmetric OH stretch plus the in-plane stretch and bend interdimer vibrations. The surface Hamiltonian is coupled to a bath of five A1g and B3g normal modes obtained at the D2h transition state structure. Eigenstates are calculated using Davidson and block-Davidson iterative methods. Strong mode specific effects are found in the tunneling splittings for the reaction surface, where splittings are enhanced upon excitation of the interdimer bend motion. The results are interpreted within the framework of a diabatic representation of reaction surface modes. The splitting patterns observed for the reaction surface eigenstates are only slightly modified upon coupling to the bath states. Splitting patterns for the bath states are also determined. It is found that predicting these splittings is greatly complicated by subtle mixings with the inter-dimer bend states.

The population lifetimes of the bend fundamental of dilute water in liquid chloroform (8.5 ps) and d-chloroform (28.5 ps) display an interesting solvent isotope effect. As the lowest excited vibrational state of the molecule, the water bend fundamental relaxes directly to the ground state with about 1600 cm-1 of energy released to the other degrees of freedom. The strong solvent isotope effect along with the large energy gap indicates the participation of solvent vibrational modes in this vibrational energy relaxation process. We calculate the vibrational energy relaxation rates of the water bend in chloroform and d-chloroform using the Landau-Teller formula with a new potential model developed and parametrized self-consistently to describe the chloroform-water interaction. The computed values are in reasonable agreement with the experimental results, and the trend for the isotope effect is correct. It is found that energy transfer to the solvent vibrations does indeed play an important role. Nevertheless, no single dominant solvent accepting mode can be identified; the relaxation appears to involve both the bend and the C-Cl stretches, and frequency changes of all of these modes upon deuteration contribute to the observed solvent isotope effect.

Molecular dynamics simulations are used in conjunction with Landau-Teller, fluctuating Landau-Teller, and time-dependent perturbation theories to investigate energy flow out of various vibrational states of liquid CHBr3 and CDBr3. The CH stretch overtone is found to relax with a time scale of about 1 ps compared to the 50 ps rate for the fundamental. The relaxation pathways and rates for the CD stretch decay in CDBr3 are computed in order to understand the changes arising from deuteration. While the computed relaxation rate agrees well with experiments, the pathway is found to be more complex than anticipated. In addition to the above channels for CH(D) stretch relaxation that involve only the hindered translations and rotations of the solvent, routes involving off-resonant and resonant excitations of solvent vibrational modes are also examined. Finally, the decay of energy from low frequency states to near-lying solute states and solvent vibrations are studied.

In continuation of our work on haloforms, the decay of CH stretch excitation in bromoform is modeled using molecular dynamics simulations. An intermolecular force field is obtained by fitting ab initio energies at select CHBr3 dimer geometries to a potential function. The solvent forces on vibrational modes obtained in the simulation are used to compute relaxation rates. The Landau-Teller approach points to a single acceptor state in the initial step of CH stretch relaxation. The time scale for this process is found to be 50-90 ps, which agrees well with the experimental value of 50 ps. The reason for the selectivity of the acceptor is elaborated. Results from a time-dependent approach to the decay rates are also discussed.

The dispersed fluorescence spectrum of the ground electronic state of thiophosgene, SCCl2, is analyzed in a very complex region of vibrational excitation, 7000-9000 cm(-1). The final result is that most of the inferred excited vibrational levels are assigned in terms of approximate constants of the motion. Furthermore, each level is associated with a rung on a ladder of quantum states on the basis of common reduced dimension fundamental motions. The resulting ladders cannot be identified by any experimental means, and it is the interspersing in energy of their rungs that makes the spectrum complex even after the process of level separation into polyads. Van Vleck perturbation theory is used to create polyad constants of the motion and a spectroscopic Hamiltonian from a potential fitted to experimental data. The eigen functions of this spectroscopic Hamiltonian are rewritten as semiclassical wave functions and transformed to a representation that allows us to analyze and assign the spectra with no other work other than to utilize concepts from nonlinear dynamics.

We calculated highly excited states of the HFCO molecule, comparing results from two methods. In the first method, Van Vleck perturbation theory is used to transform away all off-diagonal couplings except those between nearly degenerate states. This perturbative transformation leads to a matrix representation where eigenvalues are obtained with relatively small matrices. In the second method, variational eigenvalues are obtained by combining the Jacobi-Wilson approach with the block-Davidson scheme. The key ingredient here is a prediagonalized-perturbative scheme applied to a subspace of a curvilinear normal-mode basis set. Comparisons of the two methods provide a critical test of the less time-consuming perturbation theory. Two different coordinate sets are used to test the sensitivity of the results to coordinate choice. Perturbation theory also requires a polynomial fit to the potential. The implications of this restriction are investigated.

A fourth-order resonance Hamiltonian is derived from the experimental normal-mode Hamiltonian of SCCl2. The anharmonic vibrational state space constructed from the effective Hamiltonian provides a realistic model for vibrational energy flow from bright states accessible by pulsed laser excitation. We study the experimentally derived distribution PE(sigma) of dilution factors sigma as a function of energy. This distribution characterizes the dynamics in the long-time limit. State space models predict that PE(sigma) should be bimodal, with some states undergoing facile intramolecular vibrational energy redistribution (small sigma), while others at the same total energy remain "protected" (sigma approximately 1). The bimodal distribution is in qualitative agreement with analytical and numerical local density of states models. However, there are fewer states protected from energy flow, and the protected states begin to fragment at higher energy, shifting from sigma approximately 1 to sigma approximately 0.5. We also examine how dilution factors are distributed in the vibrational state space of SCCl2 and how the power law specifying the survival probability of harmonic initial states correlates with the dilution factor distribution of anharmonic initial states.

State-to-state vibrational energy relaxation (VER) rates of the OH-stretch fundamental to select vibrational modes of liquid methanol are presented. The rates are calculated via a modified, fluctuating Landau-Teller (FLT) theory approach, which allow for dynamical vibrational energy level shifts. These rates are then compared to previously published results from Gulmen and Sibert [J. Phys. Chem. A 2004, 108, 2389] for the traditional Landau-Teller (LT) method as well as results calculated through time-dependent perturbation theory (TD), which naturally allow for the fluctuation. For the first time, this method is applied to a polyatomic molecular system, and the FLT theory greatly reduces the discrepancy between the LT and TD results or, at a minimum, is comparable to the LT approach with very little additional computational cost.

A potential-energy force field for methanol is calculated at the coupled-cluster singles doubles and noniterative triples correction level using the correlation-consistent polarized valence triple zeta basis set. The force field describes the coupled molecular vibrations, including the cubic and quartic anharmonicites, as a function of the torsional coordinate. The resulting molecular eigenstates are calculated using a combination of perturbative and variation calculations following the approach of Castillo-Chará and Sibert [J. Chem. Phys. 119, 11671 (2003)]. The energies, including torsional tunneling splittings, are compared with available spectroscopic data for all the fundamentals. Excellent agreement is found. Varying the torsional mass, correlation plots are constructed in order to elucidate the complex role of torsion-vibration coupling.

The rovibrational energy levels of methane are determined from a quartic ab initio potential energy force field where the expansion coordinates are the Morse coordinates for the stretches and extension coordinates for the bends. Energies are calculated using canonical Van Vleck perturbation theory. Results are obtained for both rotation-vibration Hamiltonians expressed as functions of curvilinear and rectilinear normal coordinates. Second, fourth, and sixth order curvilinear results are compared with experimental results, and fourth order results for the rectilinear and curvilinear Hamiltonian are compared to each other. The calculated rovibrational levels are in good agreement with the experimental values for low J levels. The calculated rotational level splittings are in even better agreement with the experiment. In particular, the ground state tetrahedral splittings, which are as small as 10(-4) cm(-1), are well reproduced by our calculations at sixth order.

The IR spectra of three isotopomers of the benzoic acid dimer have been recorded under jet-cooled conditions using the double resonance method of fluorescence-dip IR spectroscopy. In so doing, the spectra are assuredly due exclusively to dimers in the ground-state zero-point level at a rotational temperature of 3-5 K. Even under these conditions, the three isotopomers have remarkably broad spectra, extending from 2600 to almost 3150 cm-1. The spectra show extensive substructure consisting of some 15-20 transitions where only a single OH stretch fundamental should appear in the harmonic limit. The comparison of the undeuterated d0-d0 dimer with the ring-deuterated d5-d5 dimer tests the effect of mixing with the C-H stretches and overtones of the C-H bends. The mixed OH/OD ring-deuterated d6-d5 dimer shifts the frequency and changes the form of the OH stretch normal mode. The analogous OH stretch IR spectrum of the d0-d0 dimer out of the S1 excited-state zero-point level has also been recorded. In this case, much of the closely-spaced substructure is not apparent. What remains is a set of three bands separated from one another by about 180 cm-1. Preliminary results of model calculations of the anharmonic coupling, responsible for the broadening and substructure, are presented. These calculations indicate that it is OH stretch-OH bend coupling, rather than coupling with the intermolecular stretch, that is responsible for much of the observed structure and breadth.