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American Chemical Society, The Journal of Physical Chemistry A, 1(118), p. 152-157, 2013

DOI: 10.1021/jp4120749

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

Journal article published in 2013 by Lasse Spoerkel, Lasse Spörkel, Ganglong Cui ORCID, Axel Koslowski, Walter Thiel ORCID
This paper is available in a repository.
This paper is available in a repository.

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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 multi-photon ionization spectroscopy. We also analyze the influence of temperature fluctuations in the initially prepared sample on the photodynamics of 7PyIn and 7PyIn-D.