First-order nonadiabatic couplings from time-dependent hybrid density functional response theory: Consistent formalism, implementation, and performance

The Journal of Chemical Physics
Robert Send, Filipp Furche

Abstract

First-order nonadiabatic coupling matrix elements (NACMEs) are key for phenomena such as nonradiative transitions and excited-state decay, yet a consistent and practical first principles treatment has been elusive for molecules with more than a few heavy atoms. Here we present theory, implementation using Gaussian basis sets, and benchmarks of first-order NACMEs between ground and excited states in the framework of time-dependent hybrid density functional theory (TDDFT). A time-dependent response approach to NACMEs which avoids explicit computation of excited-state wave functions is outlined. In contrast to previous approaches, the present treatment produces exact analytical derivative couplings between time-dependent Kohn-Sham (TDKS) determinants in a finite atom-centered basis set. As in analytical gradient theory, derivative molecular orbital coefficients can be eliminated, making the computational cost independent of the number of nuclear degrees of freedom. Our expression reduces to the exact Chernyak-Mukamel formula for first-order NACMEs in the complete basis-set limit, but greatly improves basis-set convergence in finite atom-centered basis sets due to additional Pulay type terms. The Chernyak-Mukamel formula is shown t...Continue Reading

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Citations

Oct 24, 2014·The Journal of Physical Chemistry. a·D Ondarse-AlvarezS Fernandez-Alberti
Apr 8, 2014·Accounts of Chemical Research·Zhigang ShuaiHua Geng
Dec 20, 2012·The Journal of Chemical Physics·S Fernandez-AlbertiS Tretiak
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Software Mentioned

MCSCF
TURBOMOLE
TDDFT
EGRAD
MOLPRO

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