Prediction of photodynamics of 200 nm excited cyclobutanone with linear response electronic structure and ab initio multiple spawning.

Autor:	Hait D; Department of Chemistry and The PULSE Institute, Stanford University, Stanford, California 94305, USA.; SLAC National Accelerator Laboratory, Menlo Park, California 94024, USA., Lahana D; Department of Chemistry and The PULSE Institute, Stanford University, Stanford, California 94305, USA.; SLAC National Accelerator Laboratory, Menlo Park, California 94024, USA., Fajen OJ; Department of Chemistry and The PULSE Institute, Stanford University, Stanford, California 94305, USA.; SLAC National Accelerator Laboratory, Menlo Park, California 94024, USA., Paz ASP; Department of Chemistry and The PULSE Institute, Stanford University, Stanford, California 94305, USA.; SLAC National Accelerator Laboratory, Menlo Park, California 94024, USA., Unzueta PA; Department of Chemistry and The PULSE Institute, Stanford University, Stanford, California 94305, USA.; SLAC National Accelerator Laboratory, Menlo Park, California 94024, USA., Rana B; Department of Chemistry and The PULSE Institute, Stanford University, Stanford, California 94305, USA.; SLAC National Accelerator Laboratory, Menlo Park, California 94024, USA., Lu L; Department of Chemistry and The PULSE Institute, Stanford University, Stanford, California 94305, USA.; SLAC National Accelerator Laboratory, Menlo Park, California 94024, USA., Wang Y; Department of Chemistry and The PULSE Institute, Stanford University, Stanford, California 94305, USA.; SLAC National Accelerator Laboratory, Menlo Park, California 94024, USA., Kjønstad EF; Department of Chemistry and The PULSE Institute, Stanford University, Stanford, California 94305, USA.; SLAC National Accelerator Laboratory, Menlo Park, California 94024, USA.; Department of Chemistry, Norwegian University of Science and Technology, Trondheim 7491, Norway., Koch H; Department of Chemistry, Norwegian University of Science and Technology, Trondheim 7491, Norway., Martínez TJ; Department of Chemistry and The PULSE Institute, Stanford University, Stanford, California 94305, USA.; SLAC National Accelerator Laboratory, Menlo Park, California 94024, USA.
Jazyk:	angličtina
Zdroj:	The Journal of chemical physics [J Chem Phys] 2024 Jun 28; Vol. 160 (24).
DOI:	10.1063/5.0203800
Abstrakt:	Simulations of photochemical reaction dynamics have been a challenge to the theoretical chemistry community for some time. In an effort to determine the predictive character of current approaches, we predict the results of an upcoming ultrafast diffraction experiment on the photodynamics of cyclobutanone after excitation to the lowest lying Rydberg state (S2). A picosecond of nonadiabatic dynamics is described with ab initio multiple spawning. We use both time dependent density functional theory (TDDFT) and equation-of-motion coupled cluster singles and doubles (EOM-CCSD) theory for the underlying electronic structure theory. We find that the lifetime of the S2 state is more than a picosecond (with both TDDFT and EOM-CCSD). The predicted ultrafast electron diffraction spectrum exhibits numerous structural features, but weak time dependence over the course of the simulations. (© 2024 Author(s). Published under an exclusive license by AIP Publishing.)
Databáze:	MEDLINE
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