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

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.

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Spörkel, Lasse1, Author              
Cui, Ganglong1, Author              
Koslowski, Axel1, Author              
Thiel, Walter1, Author              
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1Research Department Thiel, Max-Planck-Institut für Kohlenforschung, Max Planck Society, ou_1445590              

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 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.

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Language(s): eng - English
 Dates: 2013-12-102013-12-122014-01-09
 Publication Status: Published in print
 Pages: 6
 Publishing info: -
 Table of Contents: -
 Rev. Type: Peer
 Identifiers: DOI: 10.1021/jp4120749
 Degree: -

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Title: The Journal of Physical Chemistry A
  Other : J. Phys. Chem. A
Source Genre: Journal
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Publ. Info: Columbus, OH : American Chemical Society
Pages: - Volume / Issue: 118 (1) Sequence Number: - Start / End Page: 152 - 157 Identifier: ISSN: 1089-5639
CoNE: https://pure.mpg.de/cone/journals/resource/954926947766_4