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Lookup NU author(s): Professor Thomas Penfold
This is the authors' accepted manuscript of an article that has been published in its final definitive form by American Chemical Society, 2018.
For re-use rights please refer to the publisher's terms and conditions.
The excited-state dynamics of two functional Fe-carbene complexes, [Fe(bmip)2 ]2+ (bmip = 2,6-bis(3- methyl-imidazole-1-ylidene)-pyridine) and [Fe(btbip)2 ]2+ (btbip = 2,6-bis(3-tert -butyl-imidazole-1-ylidene)pyridine), are studied using the spin-vibronic model. In contrast to the usual projection of the ground state nuclear wave function onto an excited state surface, the dynamics are initiated by an explicit interaction term between the external time-dependent electric fi eld (laser pulse) and the transition dipole moment of the molecule. The results show that the spin-vibronic model, as constructed directly from electronic structure calculations, exhibits erroneous, polarization-dependent relaxation dynamics stemming from artifi cial interference of coupled relaxation pathways. This is due to the lack of rotational invariance in the description of excitation into degenerate states. We introduce and discuss a correction using the spherical basis and complex transition dipole moments. This modifi cation in the interaction Hamiltonian leads to rotationally invariant excitation and produces polarization-independent population dynamics.
Author(s): Papai M, Simmermacher M, Penfold TJ, Moller KB, Rozgonyi T
Publication type: Article
Publication status: Published
Journal: Journal of Chemical Theory and Computation
Year: 2018
Volume: 14
Issue: 8
Pages: 3967-3974
Print publication date: 14/08/2018
Online publication date: 25/06/2018
Acceptance date: 22/06/2018
Date deposited: 13/07/2018
ISSN (print): 1549-9618
ISSN (electronic): 1549-9626
Publisher: American Chemical Society
URL: https://doi.org/10.1021/acs.jctc.8b00135
DOI: 10.1021/acs.jctc.8b00135
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