Density functional theory of electron transfer beyond the Born-Oppenheimer approximation: Case study of LiF

The Journal of Chemical Physics
Chen LiE K U Gross

Abstract

We perform model calculations for a stretched LiF molecule, demonstrating that nonadiabatic charge transfer effects can be accurately and seamlessly described within a density functional framework. In alkali halides like LiF, there is an abrupt change in the ground state electronic distribution due to an electron transfer at a critical bond length R = Rc, where an avoided crossing of the lowest adiabatic potential energy surfaces calls the validity of the Born-Oppenheimer approximation into doubt. Modeling the R-dependent electronic structure of LiF within a two-site Hubbard model, we find that nonadiabatic electron-nuclear coupling produces a sizable elongation of the critical Rc by 0.5 bohr. This effect is very accurately captured by a simple and rigorously derived correction, with an M-1 prefactor, to the exchange-correlation potential in density functional theory, M = reduced nuclear mass. Since this nonadiabatic term depends on gradients of the nuclear wave function and conditional electronic density, ∇Rχ(R) and ∇Rn(r, R), it couples the Kohn-Sham equations at neighboring R points. Motivated by an observed localization of nonadiabatic effects in nuclear configuration space, we propose a local conditional density approximat...Continue Reading

References

Feb 7, 1997·Science·M E TuckermanM Parrinello
Apr 6, 2001·Physical Review Letters·T Kreibich, E K Gross
Jul 23, 2004·The Journal of Chemical Physics·P F WeckP C Stancil
Nov 13, 2008·Physical Review Letters·Arindam ChakrabortySharon Hammes-Schiffer
Jul 31, 2010·Journal of the American Chemical Society·Zhen CaoGregory A Voth
Sep 28, 2010·Physical Review Letters·Ali AbediE K U Gross
Jun 28, 2011·The Journal of Chemical Physics·François LiqueMillard H Alexander
Aug 18, 2012·The Journal of Chemical Physics·Yuzuru Kurosaki, Keiichi Yokoyama
Apr 17, 2013·The Journal of Physical Chemistry. a·Qunchao FanHenry F Schaefer
Jul 23, 2013·Proceedings of the National Academy of Sciences of the United States of America·Ali HassanaliMichele Parrinello
Feb 12, 2014·Philosophical Transactions. Series A, Mathematical, Physical, and Engineering Sciences·Nikitas I Gidopoulos, E K U Gross
Mar 3, 2015·The Journal of Chemical Physics·Federica AgostiniE K U Gross
Sep 19, 2015·Journal of Physics. Condensed Matter : an Institute of Physics Journal·D J CarrascalK Burke
Jul 22, 2016·The Journal of Physical Chemistry Letters·Mariana RossiDavid E Manolopoulos
Aug 9, 2016·The Journal of Chemical Physics·F G Eich, Federica Agostini
Nov 20, 2016·Physical Review Letters·Ryan Requist, E K U Gross
Jun 18, 2017·The Journal of Physical Chemistry Letters·Seung Kyu MinE K U Gross

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Citations

Apr 22, 2019·The Journal of Chemical Physics·Graeme H GosselNeepa T Maitra
Aug 1, 2018·Journal of Chemical Theory and Computation·Graeme H GosselNeepa T Maitra

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