Abstract

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.

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