Work

Interstate vibronic coupling constants between electronic excited states for complex molecules

Year: 2018

Type: article

Abstract: 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.

Source: The Journal of Chemical Physics

DOI: 10.1063/1.5022760

Authors: Maria Fumanal, Felix Plasser, Sebastian Mai, Chantal Daniel, Etienne Gindensperger

Institutions: Centre National de la Recherche Scientifique, Institut de Chimie de Strasbourg, Université de Strasbourg, University of Vienna

Language: English

Topic: Spectroscopy and Quantum Chemical Studies

Subfield: Atomic and Molecular Physics, and Optics

Field: Physics and Astronomy

Domain: Physical Sciences

Open Access status: green

Funders: Agence Nationale de la Recherche, Austrian Science Fund

Awards: Center of Chemistry of Complex System, Excited States and Dynamics of Functional Re(I) Complexes Embedded in Metalloproteins-Development of New Theoretical Methods for the Simulation and Control of Excited-State Properties and Reactivity in Biological Environments, Excited states and dynamics of functional Re(I) complexes embedded in metalloproteins