The Ehrenfest method with fully quantum nuclear motion (Qu-Eh): Application to charge migration in radical cations

An algorithm is described for quantum dynamics where an Ehrenfest potential is combined with fully quantum nuclear motion (Quantum-Ehrenfest, Qu-Eh). The method is related to the single-set variational multi-configuration Gaussian approach (vMCG) but has the advantage that only a single quantum chem...

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Bibliographic Details
Published inThe Journal of chemical physics Vol. 149; no. 9; pp. 094108 - 94117
Main Authors Jenkins, Andrew J., Spinlove, K. Eryn, Vacher, Morgane, Worth, Graham A., Robb, Michael A.
Format Journal Article
LanguageEnglish
Published United States 07.09.2018
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Summary:An algorithm is described for quantum dynamics where an Ehrenfest potential is combined with fully quantum nuclear motion (Quantum-Ehrenfest, Qu-Eh). The method is related to the single-set variational multi-configuration Gaussian approach (vMCG) but has the advantage that only a single quantum chemistry computation is required at each time step since there is only a single time-dependent potential surface. Also shown is the close relationship to the “exact factorization method.” The quantum Ehrenfest method is compared with vMCG for study of electron dynamics in a modified bismethylene-adamantane cation system. Illustrative examples of electron-nuclear dynamics are presented for a distorted allene system and for HCCI+ where one has a degenerate Π system.
ISSN:0021-9606
1089-7690
DOI:10.1063/1.5038428