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Ab initio molecular dynamics approach to tunneling splitting in polyatomic molecules
Author(s) -
Ootani Yusuke,
Taketsugu Tetsuya
Publication year - 2011
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21943
Subject(s) - intramolecular force , ab initio , quantum tunnelling , polyatomic ion , semiclassical physics , chemistry , molecule , potential energy , ab initio quantum chemistry methods , molecular dynamics , zero point energy , quantum , computational chemistry , physics , molecular physics , atomic physics , quantum mechanics
Abstract 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. © 2011 Wiley Periodicals, Inc. J Comput Chem, 2011