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Quantum Dynamics of the Excited‐State Intramolecular Proton Transfer in 2‐(2′‐Hydroxyphenyl)benzothiazole
Author(s) -
Kim Justin,
Wu Yinghua,
Brédas JeanLuc,
Batista Victor S.
Publication year - 2009
Publication title -
israel journal of chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.908
H-Index - 54
eISSN - 1869-5868
pISSN - 0021-2148
DOI - 10.1560/ijc.49.2.187
Subject(s) - chemistry , excited state , hamiltonian (control theory) , wave packet , potential energy surface , intramolecular force , quantum dynamics , benzothiazole , reaction dynamics , operator (biology) , atomic physics , quantum , quantum mechanics , computational chemistry , ab initio , physics , molecule , mathematical optimization , biochemistry , mathematics , organic chemistry , repressor , transcription factor , stereochemistry , gene
Abstract The excited‐state intramolecular proton‐transfer dynamics and photoabsorption associated with the ketoenolic tautomerization reaction in 2‐(2′‐hydr oxyphenyl)benzothiazole are simulated according to a numerically exact quantum‐dynamics propagation method and a full‐dimensional excited‐state potential energy surface based on an ab initio reaction surface Hamiltonian. The simulations involve the propagation of 69‐dimensional wave packets according to the matching‐pursuit/split‐operator Fourier transform (MP/SOFT) method (Wu, Y.; Batista, V.S. J. Chem. Phys. 2004 , 121 , 1676–1686). The underlying propagation scheme recursively applies the time‐evolution operator as defined by the Trotter expansion to second‐order accuracy in dynamically adaptive coherent‐state expansions. Computations of time‐dependent survival amplitudes, the time‐dependent product population, and photoabsorption linewidths are compared to experimental data. The reported results provide fundamental insight on the nature of the excited‐state reaction dynamics and demonstrate the capabilities of the MP/SOFT method as a powerful computational tool to study ultrafast reaction dynamics in polyatomic systems.