Diffusion Monte Carlo studies of low energy ro-vibrational states of CH5+ and its deuterated isotopologues

作者：Hinkle Charlotte E; Petit Andrew S; McCoy Anne B^*

来源：Journal of Molecular Spectroscopy, 2011, 268(1-2): 189-198.

DOI：10.1016/j.jms.2011.04.024

• Diffusion Monte Carlo
• Ro-vibrational energies, CH5+
• Deuteration effects

The lowest energy to-vibrational states of CH5+ and its deuterated isotopologues with J <= 1 are investigated using Diffusion Monte Carlo. The energies of the excited states are consistent with earlier calculations, and the rotational energies are close to the values one would obtain using vibrationally averaged rotational constants. This leads to the conclusion that at this level of excitation, rotations and vibrations are relatively decoupled. This is further verified by analysis of projections of the probability amplitudes onto various coordinates. Finally, challenges associated with applying fixed-node DMC to the evaluation of rotationally excited states of highly fluxional molecules are discussed along with strategies for addressing these challenges.

• 出版日期2011-8