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Issue 22, 2009
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A time-dependent density-functional approach to nonadiabatic electron-nucleus dynamics: formulation and photochemical application

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Abstract

To study nonadiabatic dynamics of the electrons and nuclei, the quantum chemical wavefunction methods have often been invoked to compute the nonadiabatic couplings (NACs), but time-dependent density functional theory (TD-DFT) can provide a formally exact alternative approach when the ground and one excited electronic states are concerned. Based on the density response scheme to compute the NAC vectors [J. Chem. Phys., 2007, 127, 064103], herein presented are a full quantum wave packet and a semi-classical surface hopping approach to the nonadiabatic chemical reactions for the electronically ground and excited states. The adiabatic local density approximation (ALDA) was used here but, contrary to previous simulations based on DFT or TD-DFT, no further approximations were made for the electrons. With those approaches we could successfully describe the photochemical synantiisomerization dynamics of a formaldimine molecule (CH2[double bond, length as m-dash]NH) and investigate the dissipation effects with use of a Langevin dynamics scheme. These simulations demonstrated an important role played by the dissipation and suggested that accurately modeling the dissipation is the next step towards a truly ab initio prediction.

Graphical abstract: A time-dependent density-functional approach to nonadiabatic electron-nucleus dynamics: formulation and photochemical application

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Publication details

The article was received on 20 Jan 2009, accepted on 09 Mar 2009 and first published on 26 Mar 2009


Article type: Paper
DOI: 10.1039/B901144G
Phys. Chem. Chem. Phys., 2009,11, 4570-4578

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    A time-dependent density-functional approach to nonadiabatic electron-nucleus dynamics: formulation and photochemical application

    H. Hirai and O. Sugino, Phys. Chem. Chem. Phys., 2009, 11, 4570
    DOI: 10.1039/B901144G

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