Spin-restricted descriptions of singlet oxygen reactions from XMS-CASPT2 benchmarks

Winslow, M, Hazelby, A and Robinson, D ORCID: https://orcid.org/0000-0003-2760-7163, 2024. Spin-restricted descriptions of singlet oxygen reactions from XMS-CASPT2 benchmarks. The Journal of Physical Chemistry A. ISSN 1089-5639

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Abstract

Reactions of singlet oxygen are numerous, some of which are desired but many are unwanted. Therefore, the ability to correctly predict and interpret this reactivity for complex molecular systems is essential to our understanding of singlet oxygen reactions. DFT is widely used for predicting many reactions but is not suited to degenerate electronic structures; application to isolated singlet oxygen often uses the spin-unrestricted formalism, which results in severe spin contamination. In this work, we demonstrate that spin-restricted DFT can correctly describe the reaction pathway for four prototypical singlet oxygen reactions. By careful benchmarking with XMS-CASPT2, we show that, from the first transition state onward, the degeneracy of the 1Δg state is broken due to differing interactions of the (degenerate) π* orbitals with the organic substrate; this result is well replicated with DFT. These findings demonstrate the utility of using spin-restricted DFT to explore reactions, opening the way to confidently use this computationally efficient method for molecular systems of medium to large organic molecules.

Item Type:	Journal article
Publication Title:	The Journal of Physical Chemistry A
Creators:	Winslow, M., Hazelby, A. and Robinson, D.
Publisher:	American Chemical Society
Date:	13 May 2024
ISSN:	1089-5639
Identifiers:	Number Type 10.1021/acs.jpca.4c00744 DOI 1895062 Other
Rights:	This publication is licensed under CC-BY 4.0.
Divisions:	Schools > School of Science and Technology
Record created by:	Jonathan Gallacher
Date Added:	16 May 2024 15:24
Last Modified:	16 May 2024 15:24
URI:	https://irep.ntu.ac.uk/id/eprint/51442

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