Nonadiabatic coupling vectors for excited states within time-dependent density functional theory in the Tamm-Dancoff approximation and beyond

Recently, we have proposed a scheme for the calculation of nonadiabatic couplings and nonadiabatic coupling vectors within linear response time-dependent density functional theory using a set of auxiliary many-electron wavefunctions [ I. Tavernelli, E. Tapavicza, and U. Rothlisberger, J. Chem. Phys. 130, 124107 (2009) ]. As demonstrated in a later work [ I. Tavernelli, B. F. E. Curchod, and U. Rothlisberger, J. Chem. Phys. 131, 196101 (2009) ], this approach is rigorous in the case of the calculation of nonadiabatic couplings between the ground state and any excited state. In this work, we extend this formalism to the case of coupling between pairs of singly excited states with the same spin multiplicity. After proving the correctness of our formalism using the electronic oscillator approach by Mukamel and co-workers [ S. Tretiak and S. Mukamel, Chem. Rev. (Washington, D.C.) 102, 3171 (2002) ], we tested the method on a model system, namely, protonated formaldimine, for which we computed S1/S2 nonadiabatic coupling vectors and compared them with results from high level (MR-CISD) electronic structure calculations.

Published in:
Journal of Chemical Physics, 133, 19, 194104
American Institute of Physics

 Record created 2010-12-06, last modified 2018-03-17

External link:
Download fulltext
Rate this document:

Rate this document:
(Not yet reviewed)