Correlated electron-nuclear dynamics: Exact factorization of the molecular wavefunction

Ali Abedi*, Neepa T. Maitra, E. K.U. Gross

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

201 Scopus citations

Abstract

It was recently shown [A. Abedi, N. T. Maitra, and E. K. U. Gross, Phys. Rev. Lett. 105, 123002 (2010)]10.1103/PhysRevLett.105.123002 that the complete wavefunction for a system of electrons and nuclei evolving in a time-dependent external potential can be exactly factorized into an electronic wavefunction and a nuclear wavefunction. The concepts of an exact time-dependent potential energy surface (TDPES) and exact time-dependent vector potential emerge naturally from the formalism. Here, we present a detailed description of the formalism, including a full derivation of the equations that the electronic and nuclear wavefunctions satisfy. We demonstrate the relationship of this exact factorization to the traditional Born-Oppenheimer expansion. A one-dimensional model of the H2+ molecule in a laser field shows the usefulness of the exact TDPES in interpreting coupled electron-nuclear dynamics: we show how features of its structure indicate the mechanism of dissociation. We compare the exact TDPES with potential energy surfaces from the time-dependent Hartree-approach, and also compare traditional Ehrenfest dynamics with Ehrenfest dynamics on the exact TDPES.

Original languageAmerican English
Article number22A530
JournalJournal of Chemical Physics
Volume137
Issue number22
DOIs
StatePublished - 14 Dec 2012
Externally publishedYes

Bibliographical note

Funding Information:
Partial support from the National Science Foundation (CHE-1152784) (NTM), from the Deutsche Forschungsgemeinschaft (SFB 762), and from the European Commission (FP7-NMP-CRONOS) is gratefully acknowledged.

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