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Exploring the effect of anharmonicity of molecular vibrations on thermodynamic properties.

Njegic B, Gordon MS

Department of Chemistry, Iowa State University, Ames, Iowa 50011.

Thermodynamic properties of selected small and medium size molecules were calculated using harmonic and anharmonic vibrational frequencies. Harmonic vibrational frequencies were obtained by normal mode analysis, whereas anharmonic ones were calculated using the vibrational self-consistent field (VSCF) method. The calculated and available experimental thermodynamic data for zero point energy, enthalpy, entropy, and heat capacity are compared. It is found that the anharmonicity and coupling of molecular vibrations can play a significant role in predicting accurate thermodynamic quantities. Limitations of the current VSCF method for low frequency modes have been partially removed by following normal mode displacements in internal, rather than Cartesian, coordinates.

Published 19 December 2006 in J Chem Phys, 125(22): 224102.
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