Lookup NU author(s): Dr Thomas Penfold
This work is licensed under a Creative Commons Attribution-NonCommercial 4.0 International License (CC BY-NC 4.0).
On-the-fly excited state molecular dynamics is an attractive method for studying non-equilibrium processes in excited states and is beginning to emerge as a mature approach much like its ground state counterparts. In contrast to quantum wavepacket dynamics methods, it negates the need for modelling potential energy surfaces, which usually confine nuclear motion within a reduced number of vibrational modes. In addition, on-the-fly molecular dynamics techniques are easily combined with the atomistic description of the solvents (through the QM/MM approach) allowing to explicitly address the effect of the environment. Herein, we study the nonadiabatic relaxation of photoexcited [Cu(dmp)2]+ (dmp = 2,9-dimethyl-1,10-phenanthroline) using QM/MM Trajectory Surface Hopping (TSH). We show that the decay of the initially excited singlet state into the lowest singlet (S1) state occurs within 100 fs, in agreement with previous experiments, and is slightly influenced by the nature of the solvent. Using principal component analysis (PCA), we also identify the dominant normal modes activated during the excited state decay, which are then used to design the vibrational Hamiltonian for quantum wavepacket dynamics simulations.
Author(s): Capano G, Penfold TJ, Chergui M, Tavernelli I
Publication type: Article
Publication status: Published
Journal: Physical Chemistry Chemical Physics
Print publication date: 14/08/2017
Online publication date: 23/03/2017
Acceptance date: 21/03/2017
ISSN (print): 1463-9076
ISSN (electronic): 1463-9084
Publisher: Royal Society of Chemistry
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