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How To Excite Nuclear Wavepackets into Electronically Degenerate States in Spin-Vibronic Quantum Dynamics Simulations

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.

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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.

Publication metadata

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


DOI: 10.1021/acs.jctc.8b00135


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