Disulfide bond photochemistry: the effects of higher excited states and different molecular geometries on disulfide bond cleavage

Literature Information

Publication Date 2019-01-22
DOI 10.1039/C8CP06891G
Impact Factor 3.676
Authors

Dong-Chu Chen


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Abstract

The disulfide bond is prone to ultraviolet light-induced cleavage, but the microscopic details of the light-activated bond breakage remain elusive. Here, we carry out quantum chemical calculations and the first TSH simulation of the excited state dynamics of disulfides at the MS-CASPT2 level. We demonstrate that during relaxation of the S1 state, IC to the S2 state is the predominant relaxation pathway and efficient ISC to the T2 state is geometry-dependent. Moreover, the bond cleavage leads to a strong coupling region of singlet–triplet quasidegeneracy and enlarged SOC, from which both returning to the S0 state and effective triplet formation happen. On the basis of the simulation results, the proposed electronic relaxation mechanism of light-activated disulfides is S1 → S2(T2) → region of singlet–triplet quasidegeneracy → S0, which emphasizes the competitive participation of the triplet states in the relaxation dynamics of disulfides. This theoretical work provides insights into the intrinsic excited-state properties of disulfide molecules.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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