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Far-infrared absorption spectra of water, ammonia, and chloroform calculated from instantaneous normal mode theory

J. Chem. Phys. 106, 4389 (1997); doi:10.1063/1.473486

Issue Date: 15 March 1997

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J. T. Kindt and C. A. Schmuttenmaer
Department of Chemistry, Yale University, New Haven, Connecticut 06520-8107
Instantaneous normal mode (INM) theory was used to calculate absolute far-infrared absorption spectra of water, ammonia, and chloroform. Three procedures for weighting the INM density of states to yield absorption intensities were tested against spectra based on dipole time correlation functions generated from molecular dynamics (MD) simulations. Weighting method I, which utilizes only the rotational character of a mode in determining its contribution to absorption, performed slightly better than method II, a more exact treatment which incorporates the extent to which a mode is IR-active. Method III, which includes the contributions of induced dipoles, was successful in describing the influence of induced dipoles on the far-infrared spectra of the model liquids. The contribution to absorption of unstable modes with imaginary frequencies was found to be significant at low frequencies, and was treated by a simple approximation. Agreement between INM theory and the MD analysis was quite good for chloroform and ammonia, but less so for water. Agreement with experimental data in the range of 4–100 cm−1 was generally poor, but no worse than that for the MD calculations, primarily reflecting the simple intermolecular potentials used rather than the computational method itself. ©1997 American Institute of Physics.
History: Received 24 October 1996; accepted 11 December 1996
Permalink: http://link.aip.org/link/?JCPSA6/106/4389/1
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KEYWORDS and PACS

Keywords
PACS
  • 78.30.Cp
    Optical properties, condensed matter spectroscopy and other interactions of radiation and particles with condensed matter Infrared and Raman spectra Liquids
  • 33.20.Ea
    Molecular properties and interactions with photons Molecular spectra Infrared spectra
  • 33.70.Fd
    Molecular properties and interactions with photons Intensities and shapes of molecular spectral lines and bands Absolute and relative line and band intensities
  • 02.70.Ns
    Mathematical methods in physics Computational techniques Molecular dynamics and particle methods
  • 61.20.Ja
    Structure of solids and liquids; crystallography Structure of liquids Computer simulation of liquid structure
  • 34.20.Gj
    Atomic and molecular collision processes and interactions Interatomic and intermolecular potentials and forces, potential energy surfaces for collisions Intermolecular and atommolecule potentials and forces
  • 63.50.+x
    Lattice dynamics Vibrational states in disordered systems
  • 33.20.Tp
    Molecular properties and interactions with photons Molecular spectra Vibrational analysis
  • YEAR: 1996-97

PUBLICATION DATA

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

REFERENCES (38)
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