A multidimensional semiclassical method for calculating tunneling splittings in vibrationally excited states of molecules using Cartesian coordinates is developed. It is an extension of the theory by Mil’nikov and Nakamura [J. Chem. Phys. 122, 124311 (2005)] to asymmetric paths that are necessary for calculating tunneling splitting patterns in multi-well systems, such as water clusters. Additionally, new terms are introduced in the description of the semiclassical wavefunction that drastically improves the splitting estimates for certain systems. The method is based on the instanton theory and builds the semiclassical wavefunction of the vibrationally excited states from the ground-state instanton wavefunction along the minimum action path and its harmonic neighborhood. The splittings of excited states are thus obtained at a negligible added numerical effort. The cost is concentrated, as for the ground-state splittings, in the instanton path optimization and the hessian evaluation along the path. The method can thus be applied without modification to many mid-sized molecules in full dimensionality and in combination with on-the-fly evaluation of electronic potentials. The tests were performed on several model potentials and on the water dimer.
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7 October 2020
Research Article|
October 01 2020
Tunneling splittings of vibrationally excited states using general instanton paths
Mihael Eraković
;
Mihael Eraković
Department of Physical Chemistry, Ruder Bošković Institute
, Bijenička Cesta 54, 10000 Zagreb, Croatia
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Marko T. Cvitaš
Marko T. Cvitaš
a)
Department of Physical Chemistry, Ruder Bošković Institute
, Bijenička Cesta 54, 10000 Zagreb, Croatia
a)Author to whom correspondence should be addressed: mcvitas@irb.hr
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a)Author to whom correspondence should be addressed: mcvitas@irb.hr
J. Chem. Phys. 153, 134106 (2020)
Article history
Received:
August 05 2020
Accepted:
September 08 2020
Citation
Mihael Eraković, Marko T. Cvitaš; Tunneling splittings of vibrationally excited states using general instanton paths. J. Chem. Phys. 7 October 2020; 153 (13): 134106. https://doi.org/10.1063/5.0024210
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