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We present a rigorous and comprehensive theoretical treatment of the vibrational dynamics of benzene–H2O and benzene–HDO dimers, where the quantum bound-state calculations of the coupled intra- and intermolecular vibrational states of the dimers are complemented by the quantum simulations of their infrared (IR) and Raman spectra utilizing the computed eigenstates. Apart from taking benzene to be rigid, the methodology for the nine-dimensional (9D) vibrational quantum calculations introduced in this study is fully coupled. The approach yields the intramolecular vibrational fundamentals and the bend (ν2) overtone of H2O and HDO in the complex, together with the low-lying intermolecular vibrational states in each of the intramolecular vibrational manifolds considered. Following the recently introduced general procedure [P. M. Felker and Z. Bačić, J. Chem. Phys. 151, 024305 (2019)], the full 9D vibrational Hamiltonian of the dimer is divided into a 6D intermolecular Hamiltonian, a 3D intramolecular Hamiltonian, and a 9D remainder term. A 9D contracted product basis is constructed from the low-energy eigenstates of the two reduced-dimension Hamiltonians, and the full vibrational dimer Hamiltonian is diagonalized in it. The symmetry present in the dimers is exploited to reduce the Hamiltonian matrix to a block diagonal form. Guided by the findings of our earlier study referenced above, the 6D intermolecular contracted bases for each symmetry block include only 40 eigenstates with energies up to about 225 cm−1, far below the stretch and bend fundamentals of H2O and HDO, which range between 1400 cm−1 and 3800 cm−1. As a result, the matrices representing the symmetry blocks of the 9D Hamiltonian are small for the high-dimensional quantum problem, 1360 and 1680 for the H2O and HDO complexes, respectively, allowing for direct diagonalization. These calculations characterize in detail the H2O/HDO intramolecular vibrations, their frequency shifts, and couplings to the large-amplitude-motion intermolecular vibrational sates. The computed IR spectra of the two complexes in the OH-stretch region, as well as the intermolecular Raman spectra, are compared to the experimental spectra in the literature. [ABSTRACT FROM AUTHOR]

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

Mass-selective, ionization-detected stimulated Raman spectroscopies have been applied to a study of low-frequency structure in the ground states of benzene dimer isotopomers. The results reveal two Raman bands below 10 cm-1, as well as structure in the range of 47 to 53 cm-1. Tentative assignments for the bands are proposed. [ABSTRACT FROM AUTHOR]

Theoretical and experimental results pertaining to the excitation of intermolecular vibrations in the Raman and vibronic spectra of aromatic-containing, weakly bound complexes and clusters are reported. The theoretical analysis of intermolecular Raman activity is based on the assumption that the polarizability tensor of a weakly bound species is given by the sum of the polarizability tensors of its constituent monomers. The analysis shows that the van der Waals bending fundamentals in aromatic–rare gas complexes may be expected to be strongly Raman active. More generally, it predicts strong Raman activity for intermolecular vibrations that involve the libration or internal rotation of monomer moieties having appreciable permanent polarizability anisotropies. The vibronic activity of intermolecular vibrations in aromatic-rare gas complexes is analyzed under the assumption that every vibronic band gains its strength from an aromatic-localized transition. It is found that intermolecular vibrational excitations can accompany aromatic-localized vibronic excitations by the usual Franck–Condon mechanism or by a mechanism dependent on the librational amplitude of the aromatic moiety during the course of the pertinent intermolecular vibration. The latter mechanism can impart appreciable intensity to bands that are forbidden by rigid-molecule symmetry selection rules. The applicability of such rules is therefore called into question. Finally, experimental spectra of intermolecular transitions, obtained by mass-selective, ionization-detected stimulated Raman spectroscopies, are reported for benzene–X (X=Ar, –Ar2, N2, HCl, CO2, and –fluorene), fluorobenzene–Ar and –Kr, aniline–Ar, and fluorene–Ar and –Ar2. The results support the conclusions of the theoretical analyses and provide further evidence for the value of Raman methods in characterizing intermolecular vibrational level structures. [ABSTRACT FROM AUTHOR]

Size-selective Raman spectra of carbazole–(Ar)n clusters (n=0–14) obtained between about 1305 and 1325 cm-1 by mass-selective ionization-loss stimulated Raman spectroscopy are reported. The spectra are interpreted with respect to vibrational energy flow and argon evaporation, and are compared with vibronic spectroscopic results on the species. [ABSTRACT FROM AUTHOR]

We present a perturbation theory analysis of four time-resolved fluorescence depletion schemes that are useful, or potentially useful, in rotational coherence spectroscopy. The analysis shows that ground-state rotational constants determine the rotational coherence effects in fully resonant, time-resolved stimulated Raman-induced fluorescence depletion (TRSRFD), excited-state rotational constants determine such effects in time-resolved stimulated emission spectroscopy (TRSES), and both ground- and excited-state constants do so in time-resolved fluorescence depletion (TRFD). An analysis of a variant of the TRSRFD scheme in which the stimulated Raman process is not resonance-enhanced shows that this method gives rise to qualitatively different rotational coherence effects than fully resonant TRSRFD. It is argued that the scheme may, nevertheless, be a viable means of ground-state rotational coherence spectroscopy. Expressions for the calculation of rotational coherence effects in TRFD, TRSRFD, and TRSES traces are also presented. Such expressions are used to show that the magnitudes of rotational coherence transients are similar in all three schemes. Finally, experimental results on molecular iodine are presented to show that, indeed, both ground- and excited-state rotational coherence effects are manifest in TRFD traces. [ABSTRACT FROM AUTHOR]

A perturbation theory analysis of Fourier transform (interferometric) versions of coherent Raman scattering and ionization-detected (or fluorescence-detected) stimulated Raman scattering is presented. The analysis has the principal aim of examining the information content of these spectroscopies as a function of the temporal characteristics of the excitation fields. The general conclusion of the analysis is that the information content of the techniques does not depend on excitation pulsewidths and, in particular, that spectral resolution is not limited by such pulsewidths. This is an important result because it allows for the use of short-pulse laser systems in implementing the methods. It is also shown, however, that the temporal characteristics of the excitation fields do influence the practical implementations of the spectroscopies significantly in that signal-to-noise ratios, Doppler broadening, etc. can be dependent on these characteristics. [ABSTRACT FROM AUTHOR]

We report the results of nonlinear Raman spectroscopy measurements of intermolecular transitions in the hydrogen-bonded complexes 1-naphthol-H[sub 2]O and 1-naphthol-NH[sub 3]. Bands are assigned, primarily by pendular band-contour analysis and by reference to calculated results from Knochenmuss et al. [J. Phys. Chem. 102, 1935 (1998)], to transitions involving the three hydrogen-bond vibrations in which there is relative translational motion between the two molecules in the complex. Splittings due to tunneling between hydrogen-bond torsional states are also identified. © 2000 American Institute of Physics. [ABSTRACT FROM AUTHOR]