A FULL-DIMENSIONAL SEMICLASSICAL CALCULATION OF VIBRATIONAL-MODE SELECTIVITY IN THE TUNNELING SPLITTING IN A PLANAR MODEL OF MALONALDEHYDE

被引：30

作者：

GUO, Y

SEWELL, TD

THOMPSON, DL

机构：

[1] Department of Chemistry, Oklahoma State University, Stillwater

来源：

CHEMICAL PHYSICS LETTERS | 1994年 / 224卷 / 5-6期

关键词：

D O I：

10.1016/0009-2614(94)00587-7

中图分类号：

O64 [物理化学（理论化学）、化学物理学];

学科分类号：

070304 ; 081704 ;

摘要：

A semiclassical method is used to treat proton tunneling in a planar model of malonaldehyde. Classical trajectories were calculated on a realistic potential-energy surface and WKB tunneling probabilities were calculated at turning points on the barrier separating the two equivalent potential wells. The calculated ground-state splitting, 24.5 cm-1, is in good agreement with the experimental value of 21.6 cm-1. Vibrational mode selectivity was studied by calculating the splitting for all 15 modes for 2 kcal/mol excitation energy (35 kcal/mol total energy). The results show significant mode specific effects for all except some C-H stretching modes. This study demonstrates that multidimensional semiclassical tunneling can be readily and accurately treated.

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页码：470 / 475

页数：6

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