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Creators/Authors contains: "Varganov, Sergey A."

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  1. In this article, we review nonadiabatic molecular dynamics (NAMD) methods for modeling spin-crossover transitions. First, we discuss different representations of electronic states employed in the grid-based and direct NAMD simulations. The nature of interstate couplings in different representations is highlighted, with the main focus on nonadiabatic and spin-orbit couplings. Second, we describe three NAMD methods that have been used to simulate spin-crossover dynamics, including trajectory surface hopping, ab initio multiple spawning, and multiconfiguration time-dependent Hartree. Some aspects of employing different electronic structure methods to obtain information about potential energy surfaces and interstate couplings for NAMD simulations are also discussed. Third, representative applications of NAMD to spin crossovers in molecular systems of different sizes and complexities are highlighted. Finally, we pose several fundamental questions related to spin-dependent processes. These questions should be possible to address with future methodological developments in NAMD. 
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  2. null (Ed.)
    An understanding of the role that spin states play in semiconductor surface chemical reactions is currently limited. Herein, we provide evidence of a nonadiabatic reaction involving a localized singlet to triplet thermal excitation of the Si(100) surface dimer dangling bond. By comparing the β-hydrogen elimination kinetics of ethyl adsorbates probed by thermal desorption experiments to electronic structure calculation results, we determined that a coverage-dependent change in mechanism occurs. At low coverage, a nonadiabatic, inter-dimer mechanism is dominant, while adiabatic mechanisms become dominant at higher coverage. Computational results indicate that the spin crossover is rapid near room temperature and the nonadiabatic path is accelerated by a barrier that is 40 kJ mol −1 less than the adiabatic path. Simulated thermal desorption reactions using nonadiabatic transition state theory (NA-TST) for the surface dimer intersystem crossing are in close agreement with experimental observations. 
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  3. null (Ed.)
    The T 1 excited state relaxation in thiophosgene has attracted much attention as a relatively simple model for the intersystem crossing (ISC) transitions in polyatomic molecules. The very short (20–40 ps) T 1 lifetime predicted in several theoretical studies strongly disagrees with the experimental values (∼20 ns) indicating that the kinetics of T 1 → S 0 ISC is not well understood. We use the nonadiabatic transition state theory (NA-TST) with the Zhu–Nakamura transition probability and the multireference perturbation theory (CASPT2) to show that the T 1 → S 0 ISC occurs in the quantum tunneling regime. We also introduce a new zero-point vibrational energy correction scheme that improves the accuracy of the predicted ISC rate constants at low internal energies. The predicted lifetimes of the T 1 vibrational states are between one and two orders of magnitude larger than the experimental values. This overestimation is attributed to the multidimensional nature of quantum tunneling that facilitates ISC transitions along the non-minimum energy path and is not accounted for in the one-dimensional NA-TST. 
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  4. null (Ed.)