A Vibronic Coupling Hamiltonian to Describe the Ultrafast Excited State Dynamics of a Cu(I)-Phenanthroline Complex

Authors

  • Gloria Capano Laboratory of Computational Chemistry and Biochemistry Ecole Polytechnique Fédérale de Lausanne CH-1015 Lausanne, Switzerland; Laboratory of Ultrafast Spectroscopy Ecole Polytechnique Fédérale de Lausanne CH-1015 Lausanne, Switzerland
  • Thomas J. Penfold SwissFEL Paul Scherrer Institute CH-5232 Villigen, Switzerland. thomas.penfold@psi.ch
  • Ursula Röthlisberger Laboratory of Computational Chemistry and Biochemistry Ecole Polytechnique Fédérale de Lausanne CH-1015 Lausanne, Switzerland
  • Ivano Tavernelli Laboratory of Computational Chemistry and Biochemistry Ecole Polytechnique Fédérale de Lausanne CH-1015 Lausanne, Switzerland

DOI:

https://doi.org/10.2533/chimia.2014.227

Keywords:

Cu(i)-phenanthroline complex, Multi-configuration time-dependent hartree, Nonadiabatic, Vibronic coupling hamiltonian, Time-dependent density functional theory

Abstract

We present a model Hamiltonian to study the nonadiabatic dynamics of photoexcited [Cu(dmp)2]+, (dmp = 2,9-dimethyl-1,10-phenanthroline). The relevant normal modes, identified by the magnitude of the first order coupling constants, correspond closely to those observed experimentally. The potential energy surfaces (PES) and nonadiabatic couplings for these modes are computed and provide a first interpretation of the nonadiabatic relaxation mechanism. The Hamiltonian incorporates both the low lying singlet and triplet states, which will make it possible to follow the dynamics from the photoexcitation event to the initial stages of intersystem crossing.
CHIMIA Vol. 68 No. 4(2014): Laureates of the SCS Fall Meeting 2013

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Published

2014-04-30

Issue

Vol. 68 No. 4 (2014): Laureates of the SCS Fall Meeting 2013

Section

Scientific Articles

License

Copyright (c) 2014 Swiss Chemical Society

Creative Commons License

This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License.

How to Cite

[1]
G. Capano, T. J. Penfold, U. Röthlisberger, I. Tavernelli, Chimia 2014, 68, 227, DOI: 10.2533/chimia.2014.227.