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Updated: Apr 27, 2026

Excitonic Hamiltonians for Calculating Optical Absorption Spectra and Optoelectronic Properties of Molecular Aggregates and Solids
Published on: May 27, 2020
A vibronic coupling hamiltonian to describe the ultrafast excited state dynamics of a Cu(i)-phenanthroline complex
Gloria Capano1, Thomas J Penfold2, Ursula Röthlisberger3
1Laboratory 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.
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.
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