Issue 32, 2024

Nonadiabatic molecular dynamics simulations shed light on the timescale of furylfulgide photocyclisation

Abstract

The sequence of events during the photocyclisation of furylfulgides is not fully understood, and there is a significant disparity between ring closing timescales determined with the use of transient absorption spectroscopy [Siewertsen et al., Phys. Chem. Chem. Phys., 2011, 13, 3800] and the timescale estimated on the basis of nonadiabatic molecular dynamics (NAMD) simulations [Kochman et al., Phys. Chem. Chem. Phys., 2022, 24, 18103]. With a view to resolving this issue, in the present study I report NAMD simulations of the photorelaxation process of a model furylfulgide with a bulky alkyl substituent at carbon atom C3. I employed a pattern recognition algorithm in order to automate the analysis of the simulated trajectories. According to the simulation results, the bulky alkyl group causes a substantial increase in the photocyclisation quantum yield, but the timescale of ring closing is only marginally affected. I discuss the implications of these findings in light of the available spectroscopic data.

Graphical abstract: Nonadiabatic molecular dynamics simulations shed light on the timescale of furylfulgide photocyclisation

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Article information

Article type
Paper
Submitted
12 Oct 2023
Accepted
19 Jul 2024
First published
19 Jul 2024
This article is Open Access
Creative Commons BY license

New J. Chem., 2024,48, 14327-14335

Nonadiabatic molecular dynamics simulations shed light on the timescale of furylfulgide photocyclisation

M. A. Kochman, New J. Chem., 2024, 48, 14327 DOI: 10.1039/D3NJ04752K

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