Intricate Spin-Vibronic Dynamics and Excited-State Intramolecular Thiol Proton Transfer in Dithiotropolone

IF 3.4 3区化学 Q2 CHEMISTRY, MULTIDISCIPLINARY

Journal of Computational Chemistry Pub Date : 2025-03-31 DOI:10.1002/jcc.70094

Anshuman Bera, Sivaranjana Reddy Vennapusa

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Abstract

We perform a computational investigation to unravel the mechanisms of intramolecular thiol proton transfer and triplet formation in dithiotropolone. The S₁ and S₂ states are dipole-forbidden, whereas S₃ and S₄ are dipole-allowed states in this molecule. Upon initiating the nuclear wavepacket on S₃, this molecule exhibits simultaneous S₃ to S₂/S₁ internal conversion and S₃-T₄ intersystem crossing. Further simulations reveal that the molecule shows ultrafast internal conversion in the triplet manifold, similar to its singlet dynamics. Apart from these decay processes in the Franck-Condon region, this molecule can display thiol proton transfer via multiple singlet states due to low barrier energies along the reaction coordinate. The S₁-T₄ and S₃-T₅/T₆ crossings upon the S-H coordinate's elongation illustrate that the molecule can also show the triplet formation outside the Franck-Condon region.

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来源期刊

Journal of Computational Chemistry 化学-化学综合

CiteScore

6.60

自引率

3.30%

发文量

247

审稿时长

1.7 months

期刊介绍： This distinguished journal publishes articles concerned with all aspects of computational chemistry: analytical, biological, inorganic, organic, physical, and materials. The Journal of Computational Chemistry presents original research, contemporary developments in theory and methodology, and state-of-the-art applications. Computational areas that are featured in the journal include ab initio and semiempirical quantum mechanics, density functional theory, molecular mechanics, molecular dynamics, statistical mechanics, cheminformatics, biomolecular structure prediction, molecular design, and bioinformatics.