Instanton theory for the tunneling splitting of low vibrationally excited states

We develop the instanton theory for calculating the tunneling splitting of excited states. For the case of low vibrational quantum states we derive a canonically invariant formula which is applicable to a multidimensional system of arbitrary Riemannian metric. The effect of multidimensionality in re...

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Bibliographic Details
Published in:The Journal of chemical physics 2005-03, Vol.122 (12), p.124311-124311
Main Authors: Mil'nikov, Gennady V, Nakamura, Hiroki
Format: Article
Language:English
Subjects:
Free Radicals - chemistry
Models, Theoretical
Quantum Theory
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Summary:We develop the instanton theory for calculating the tunneling splitting of excited states. For the case of low vibrational quantum states we derive a canonically invariant formula which is applicable to a multidimensional system of arbitrary Riemannian metric. The effect of multidimensionality in relation to the vibrational excitation is explained in terms of the effective frequencies along the instanton trajectory. The theory is demonstrated to work well by taking HO2 molecule as an example.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.1869989