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Updated: Jun 6, 2026
Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
Nonadiabatic coupling vectors for excited states within time-dependent density functional theory in the Tamm-Dancoff
Ivano Tavernelli1, Basile F E Curchod, Andrey Laktionov
1Laboratory of Computational Chemistry and Biochemistry, Ecole Polytechnique Fédérale de Lausanne, Lausanne CH-1015, Switzerland. ivano.tavernelli@epfl.ch
Abstract:
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 S(1)/S(2) nonadiabatic coupling vectors and compared them with results from high level (MR-CISD) electronic structure calculations.
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