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Journal Article

Nonequilibrium H/D Isotope Effects from Trajectory-Based Nonadiabatic Dynamics

MPS-Authors
http://pubman.mpdl.mpg.de/cone/persons/resource/persons104510

Spörkel,  Lasse
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons58498

Cui,  Ganglong
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons58716

Koslowski,  Axel
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

http://pubman.mpdl.mpg.de/cone/persons/resource/persons59045

Thiel,  Walter
Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society;

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Supplementary Material (public)

jp4120749_si_001.pdf
(Supplementary material), 2MB

Citation

Spörkel, L., Cui, G., Koslowski, A., & Thiel, W. (2014). Nonequilibrium H/D Isotope Effects from Trajectory-Based Nonadiabatic Dynamics. The Journal of Physical Chemistry A, 118(1), 152-157. doi:10.1021/jp4120749.


Cite as: http://hdl.handle.net/11858/00-001M-0000-0018-B299-7
Abstract
Ground-state equilibrium kinetic isotope effects can be treated well in the framework of transition state theory, whereas excited-state nonequilibrium isotope effects are theoretically less explored. In this article we show for the first time that trajectory-based nonadiabatic dynamics simulations are able to reproduce experimental values for nonequilibrium H/D isotope effects in excited-state processes. We use high-level electronic structure calculations (MS-CASPT2, DFT/MRCI, and TDDFT) and full-dimensional OM2/MRCI-based nonadiabatic dynamics simulations to study the ultrafast intramolecular excited-state proton transfer (ESIPT) and the subsequent deactivation of 7-(2-pyridyl)indole (7PyIn) and its deuterated analogue (7PyIn-D). We evaluate a total of 1367 surface-hopping trajectories to establish the differences in the dynamical behavior of 7PyIn and 7PyIn-D. The computed H/D isotope effects for ESIPT and excited-state decay are consistent with recent experimental results from femtosecond pump–probe resonance-enhanced multiphoton ionization spectroscopy. We also analyze the influence of temperature fluctuations in the initially prepared sample on the photodynamics of 7PyIn and 7PyIn-D.