Wave packet dynamics in the optimal superadiabatic approximation

V. Betz, Benjamin Goddard, U. Manthe

Research output: Contribution to journalArticlepeer-review

Abstract

We explain the concept of superadiabatic representations and show how in the context of electronically nonadiabatic transitions they lead to an explicit formula that can be used to predict transitions at avoided crossings. Based on this formula, we present a simple method for computing wave packet dynamics across avoided crossings. Only knowledge of the adiabatic potential energy surfaces near the avoided crossing is required for the computation. In particular, this means that no diabatization procedure is necessary, the adiabatic electronic energies can be computed on the y, and they only need to be computed to higher accuracy when an avoided crossing is detected. We test the quality of our method on the paradigmatic example of photo-dissociation of NaI, finding very good agreement with results of exact wave packet calculations.
Original languageEnglish
Article number224109
Number of pages13
JournalJournal of Chemical Physics
Volume144
Issue number22
DOIs
Publication statusPublished - 14 Jun 2016

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