Converged quantum dynamics calculations of vibrational energies of CH4 and CH3D using an ab initio potential. 2004

Hua-Gen Yu
Department of Chemistry, Brookhaven National Laboratory, Upton, New York 11973-5000, USA. hgy@bnl.gov

Exact variational calculations of vibrational energies of CH4 and CH3D are carried out using a two-layer Lanczos algorithm based on the ab initio potential energy surface of D. W. Schwenke and H. Partridge, Spectrochim. Acta, Part A 57, 887 (2001). The convergence of the calculated vibrational energies is discussed in detail. In addition, we report all well converged vibrational energy levels up to 6600 cm(-1) for CH4, and those up to 5000 cm(-1) for CH3D, respectively. These results clearly outperform previous theoretical calculations. And a comparison with experimental results available is also made.

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