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

Mátyás Pápai*, Mats Simmermacher, Thomas James Penfold, Klaus Braagaard Møller, Tamas Rozgonyi

*Corresponding author for this work

Research output: Contribution to journalJournal articleResearchpeer-review

26 Downloads (Pure)

Abstract

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 wavefunction onto an excited state surface, the dynamics are initiated by an explicit interaction term between the external time-dependent electric field (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 artificial 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 modification in the Hamiltonian leads to rotationally invariant excitation and produces polarization-independent population dynamics.

Original languageEnglish
JournalJournal of Chemical Theory and Computation
Volume12
Issue number8
Pages (from-to)3967-3974
Number of pages8
ISSN1549-9618
DOIs
Publication statusPublished - 2018

Cite this

@article{fa23ab73a29e4f61b576e2578c24053d,
title = "How to Excite Nuclear Wavepackets into Electronically Degenerate States in Spin-Vibronic Quantum Dynamics Simulations",
abstract = "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 wavefunction onto an excited state surface, the dynamics are initiated by an explicit interaction term between the external time-dependent electric field (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 artificial 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 modification in the Hamiltonian leads to rotationally invariant excitation and produces polarization-independent population dynamics.",
author = "M{\'a}ty{\'a}s P{\'a}pai and Mats Simmermacher and Penfold, {Thomas James} and M{\o}ller, {Klaus Braagaard} and Tamas Rozgonyi",
year = "2018",
doi = "10.1021/acs.jctc.8b00135",
language = "English",
volume = "12",
pages = "3967--3974",
journal = "Journal of Chemical Theory and Computation",
issn = "1549-9618",
publisher = "American Chemical Society",
number = "8",

}

How to Excite Nuclear Wavepackets into Electronically Degenerate States in Spin-Vibronic Quantum Dynamics Simulations. / Pápai, Mátyás; Simmermacher, Mats; Penfold, Thomas James; Møller, Klaus Braagaard; Rozgonyi, Tamas.

In: Journal of Chemical Theory and Computation, Vol. 12, No. 8, 2018, p. 3967-3974.

Research output: Contribution to journalJournal articleResearchpeer-review

TY - JOUR

T1 - How to Excite Nuclear Wavepackets into Electronically Degenerate States in Spin-Vibronic Quantum Dynamics Simulations

AU - Pápai, Mátyás

AU - Simmermacher, Mats

AU - Penfold, Thomas James

AU - Møller, Klaus Braagaard

AU - Rozgonyi, Tamas

PY - 2018

Y1 - 2018

N2 - 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 wavefunction onto an excited state surface, the dynamics are initiated by an explicit interaction term between the external time-dependent electric field (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 artificial 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 modification in the Hamiltonian leads to rotationally invariant excitation and produces polarization-independent population dynamics.

AB - 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 wavefunction onto an excited state surface, the dynamics are initiated by an explicit interaction term between the external time-dependent electric field (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 artificial 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 modification in the Hamiltonian leads to rotationally invariant excitation and produces polarization-independent population dynamics.

U2 - 10.1021/acs.jctc.8b00135

DO - 10.1021/acs.jctc.8b00135

M3 - Journal article

VL - 12

SP - 3967

EP - 3974

JO - Journal of Chemical Theory and Computation

JF - Journal of Chemical Theory and Computation

SN - 1549-9618

IS - 8

ER -