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Incorporating Spin–Orbit Effects into Surface Hopping Dynamics Using the Diagonal Representation: A Linear-Response Time-Dependent Density Functional Theory Implementation with Applications to 2-Thiouracil

Abstract

In this study, we present a trajectory surface hopping (TSH) method that incorporates spin-orbit (SO) effects using “diagonal representation” within Linear-Response Time-Dependent Density Functional Theory (LR-TDDFT) framework. In this approach, the evaluation of spin-orbit coupling (SOC) matrix elements between singlet and triplet states employs the Casida’s wave functions and the Breit-Pauli (BP) spin−orbit Hamiltonian with effective charge approximation. The new TSH approach is then used to investigate the excited-state relaxation of 2-thiouracil (2TU) in vacuum and water. On the basis of the simulation results, relaxation of the initially populated bright state is found to be dominated by the route S2 → S1 → T. The intersystem crossing (ISC) can occur at either the C2-puckered structure or the C2-pyramidalized S1 minimum, and is promoted by a three-state near-degeneracy (S1/T2/T1 in vacuum or S1/T3/T2 in water) as well as sizable SOCs. Our simulations achieve a good agreement with the available experimental measurements in terms of the internal conversion (IC) and ISC time scales, and complement the picture of the relaxation mechanisms of 2TU after photo-excitation to the first bright state.

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Publication details

The article was received on 22 Mar 2018, accepted on 08 May 2018 and first published on 08 May 2018


Article type: Paper
DOI: 10.1039/C8CP01852A
Citation: Phys. Chem. Chem. Phys., 2018, Accepted Manuscript
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    Incorporating Spin–Orbit Effects into Surface Hopping Dynamics Using the Diagonal Representation: A Linear-Response Time-Dependent Density Functional Theory Implementation with Applications to 2-Thiouracil

    J. Duan, Y. Zhou, Z. Xie, T. Sun and J. cao, Phys. Chem. Chem. Phys., 2018, Accepted Manuscript , DOI: 10.1039/C8CP01852A

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