Interstate vibronic coupling constants between electronic excited states for complex molecules
journal contributionposted on 04.04.2018 by Maria Fumanal, Felix Plasser, Sebastian Mai, Chantal Daniel, Etienne Gindensperger
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In the construction of diabatic vibronic Hamiltonians for quantum dynamics in the excited-state manifold of molecules, the coupling constants are often extracted solely from information on the excited-state energies. Here, a new protocol is applied to get access to the interstate vibronic coupling constants at the time-dependent density functional theory level through the overlap integrals between excited-state adiabatic auxiliary wavefunctions. We discuss the advantages of such method and its potential for future applications to address complex systems, in particular, those where multiple electronic states are energetically closely lying and interact. We apply the protocol to the study of prototype rhenium carbonyl complexes [Re(CO)3(N,N)(L)]n+ for which non-adiabatic quantum dynamics within the linear vibronic coupling model and including spin-orbit coupling have been reported recently.
M.F., C.D., and E.G. acknowledge funding from the Agence Nationale de la Recherche within Project Nos. ANR-10-LABX-0026 (Chimie des Systemes Complexes) and ANR-15-CE29-0027-01 (DeNeTheor) as well as the Frontier Research in Chemistry Foundation, Strasbourg. F.P. and S.M. acknowledge funding from the Austrian Science Fund (FWF) within Project No. I2883 (DeNeTheor) and the University of Vienna, as well as the Vienna Scientific Cluster (VSC) for generous allocation of computing time. Support from the COST action CM1305 (ECostBio) is acknowledged.