In the current study, we present nonadiabatic (NAMD) and adiabatic molecular dynamics simulations of the transition-state dynamics of photoexcited cyclooctatetraene (COT). The equilibrium-state structure and absorption spectra are analyzed using the semiempirical Austin Model 1 potential. The NAMD simulations are obtained by a surface-hopping algorithm. We analyzed in detail an active excited to ground state relaxation pathway accompanied by anS2/S3(D2d) →S1(D8h) →S0(D4h) →S0(D2d) double-bond shifting mechanism. The simulated excitation lifetime is in good agreement with experiment. The first excited singlet stateS1plays a crucial role in the photochemistry. The obtained critical molecular conformations, energy barrier, and transition-state lifetime results will provide a basis for further investigations of the bond-order inversion and photoswitching process of COT.

Nonadiabatic Molecular Dynamics Study of the Relaxation Pathways of Photoexcited Cyclooctatetraene

Garavelli M.;
2021

Abstract

In the current study, we present nonadiabatic (NAMD) and adiabatic molecular dynamics simulations of the transition-state dynamics of photoexcited cyclooctatetraene (COT). The equilibrium-state structure and absorption spectra are analyzed using the semiempirical Austin Model 1 potential. The NAMD simulations are obtained by a surface-hopping algorithm. We analyzed in detail an active excited to ground state relaxation pathway accompanied by anS2/S3(D2d) →S1(D8h) →S0(D4h) →S0(D2d) double-bond shifting mechanism. The simulated excitation lifetime is in good agreement with experiment. The first excited singlet stateS1plays a crucial role in the photochemistry. The obtained critical molecular conformations, energy barrier, and transition-state lifetime results will provide a basis for further investigations of the bond-order inversion and photoswitching process of COT.
Song H.; Nam Y.; Keefer D.; Garavelli M.; Mukamel S.; Tretiak S.
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Utilizza questo identificativo per citare o creare un link a questo documento: https://hdl.handle.net/11585/845997
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