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Condensed phase spectroscopy from mixed-order semiclassical molecular dynamics: Absorption, emission, and resonant Raman spectra of I2 isolated in solid Kr
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The collisional removal of O2 molecules in selected vibrational levels of the c 1 - u" align="middle"/> state is studied using a two-laser double-resonance technique. The output of the first laser exc...

Vibrational wave functions and spectroscopy of (H2O)n, n=2,3,4,5: Vibrational self-consistent field with correlation corrections

J. Chem. Phys. 105, 10332 (1996); doi:10.1063/1.472960

Issue Date: 15 December 1996

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Joon O. Jung
Department of Chemistry, University of California, Irvine, California 92697-2025

R. Benny Gerber
Department of Chemistry, University of California, Irvine, California 92697-2025
Department of Physical Chemistry and The Fritz Haber Research Center, The Hebrew University, Jerusalem, 91904, Israel
Vibrational energy levels, wave functions, and ir absorption intensities are computed for (H2O)n clusters with n=2, 3, 4, and 5. The calculations were carried out by the vibrational self-consistent field (VSCF) approximation, with corrections for correlations between the modes by perturbation theory. This correlation corrected VSCF (CC-VSCF) is analogous to the familiar Möller–Plesset method in electronic structure theory. Test calculations indicate that this method is of very good accuracy also for very anharmonic systems. While the method is of highest relative accuracy for the stiffest modes, it works very well also for the soft ones. Some of the main results are (1) the frequencies calculated are in good but incomplete agreement with experimental data available for some of the intramolecular mode excitations. The deviations are attributed to the inaccuracy of the coupling between intramolecular and intermolecular modes for the potential function used. (2) Insight is gained into the pattern of blue- or redshifts from the corresponding harmonic excitation energies for the various modes. (3) Anharmonic coupling between the modes dominates in general over the intrinsic anharmonicity of individual modes in determining the spectrum. (4) The anharmonic corrections to the frequencies of some intermolecular modes (shearing, torsional) are extremely large, and exceed 100% or more in many cases. (5) An approximation of quartic potential field in the normal mode displacement is tested for the clusters. It works well for the high and intermediate frequency modes, but is in error for very soft shearing and torsional modes. (6) The relative errors of the VSCF approximation are found to decrease with the cluster size. This is extremely encouraging for calculations of large clusters, since the VSCF level is computationally simple. ©1996 American Institute of Physics.
History: Received 23 August 1996; accepted 12 September 1996
Permalink: http://link.aip.org/link/?JCPSA6/105/10332/1
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KEYWORDS and PACS

Keywords
PACS
  • 36.40.Mr
    Studies of special atoms, molecules, and their ions; clusters Atomic and molecular clusters Spectroscopy and geometrical structure of clusters
  • 33.20.Ea
    Molecular properties and interactions with photons Molecular spectra Infrared spectra
  • 31.15.Ne
    Electronic structure of atoms, molecules and their ions: theory Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Self-consistent-field methods
  • YEAR: 1996

PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
Publisher:
AIP is a member of CrossRef AIP

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