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Efficient evaluation of the accuracy of molecular quantum dynamics on an approximate analytical or interpolated ab initio potential energy surface
Author(s) -
Zimmermann Tomáš,
Ruppen Julien,
Li Baiqing,
Vaníček Jiří
Publication year - 2010
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.22730
Subject(s) - ab initio , potential energy surface , quantum dynamics , semiclassical physics , potential energy , quantum , excited state , morse potential , electronic structure , ab initio quantum chemistry methods , molecular dynamics , physics , statistical physics , quantum mechanics , chemistry , molecule
Ab initio electronic structure methods have reached a satisfactory accuracy for the calculation of static properties, but remain too expensive for quantum dynamical calculations. Recently, an efficient semiclassical method was proposed to evaluate the accuracy of quantum dynamics on an approximate potential without having to perform the expensive quantum dynamics on the accurate potential. Here, this method is applied for the first time to evaluate the accuracy of quantum dynamics on an approximate analytical or interpolated potential in comparison to the quantum dynamics on an accurate potential obtained by an ab initio electronic structure method. Specifically, the vibrational dynamics of H 2 on a Morse potential is compared with that on the full CI potential, and the photodissociation dynamics of CO 2 on a LEPS potential with that on the excited 1 Π surface computed at the EOM‐CCSD/aug‐cc‐pVDZ level of theory. Finally, the effect of discretization of a potential energy surface on the quantum dynamics is evaluated. © 2010 Wiley Periodicals, Inc. Int J Quantum Chem 110:2426–2435, 2010