Nonadiabatic dynamics with intersystem crossings: A time-dependent density functional theory implementation

Journal Article · Mon Dec 14 04:00:00 EST 2015 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4936864· OSTI ID:22493301

Franco de Carvalho, F. ^[1]; Tavernelli, I. ^[2]

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1. Centre Européen de Calcul Atomique et Moléculaire, Ecole Polytechnique Fédérale de Lausanne, Lausanne (Switzerland)
2. IBM Research GmbH, Zurich Research Laboratory, 8803 Ruschlikon (Switzerland)

In this work, we derive a method to perform trajectory-based nonadiabatic dynamics that is able to describe both nonadiabatic transitions and intersystem crossing events (transitions between states of different spin-multiplicity) at the same level of theory, namely, time-dependent density functional theory (TDDFT). To this end, we combined our previously developed TDDFT-based trajectory surface hopping scheme with an accurate and efficient algorithm for the calculation of the spin-orbit coupling (SOC) matrix elements. More specifically, we designed two algorithms for the calculation of intersystem crossing transitions, one based on an extended Tully’s surface hopping scheme including SOC and the second based on a Landau-Zener approximation applied to the spin sector of the electronic Hilbert space. This development allows for the design of an efficient on-the-fly nonadiabatic approach that can handle, on an equal footing, nonadiabatic and intersystem crossing transitions. The method is applied to the study of the photophysics of sulfur dioxide (SO{sub 2}) in gas and liquid phases.

• OSTI ID: 22493301
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 22 Vol. 143; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
ALGORITHMS
DENSITY FUNCTIONAL METHOD
HILBERT SPACE
IMPLEMENTATION
L-S COUPLING
LANDAU-ZENER FORMULA
LIQUIDS
MATRIX ELEMENTS
MULTIPLICITY
SPIN
SULFUR DIOXIDE
SURFACES
TIME DEPENDENCE