Ab Initio Molecular Dynamics Approach to Tunneling Splitting in Polyatomic Molecules

作者：Ootani Yusuke^*; Taketsugu Tetsuya

来源：Journal of Computational Chemistry, 2012, 33(1): 60-65.

DOI：10.1002/jcc.21943

• ab initio molecular dynamics
• tunneling splitting
• intramolecular hydrogen transfer in malonaldehyde

An ab initio molecular dynamics approach is combined with the semiclassical tunneling method of Makri and Miller, which is applied to estimations of tunneling splitting in the umbrella inversion of ammonia and the intramolecular hydrogen transfer in malonaldehyde. In the application to malonaldehyde, effects of multidimensionality are examined by assigning quantum zero-point energies only to significant vibrational modes and changing the amount of energy given to other degrees of freedom. The calculated tunneling splitting values are in good agreement with the corresponding experimental values for both molecules.

• 出版日期2012-1-5