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A theoretical investigation on the excited state intramolecular single or double proton transfer mechanism of a salicyladazine system
Author(s) -
Zhang Qiaoli,
Zhao Zhongjian,
Cheng Shibo,
Yang Guang,
Zhang Tianjie,
Jia Min,
Song Xiaoyan
Publication year - 2019
Publication title -
journal of the chinese chemical society
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.329
H-Index - 45
eISSN - 2192-6549
pISSN - 0009-4536
DOI - 10.1002/jccs.201800490
Subject(s) - intramolecular force , chemistry , excited state , time dependent density functional theory , density functional theory , molecular orbital , molecule , hydrogen bond , chemical physics , proton , redistribution (election) , atomic orbital , potential energy surface , computational chemistry , atomic physics , photochemistry , electron , stereochemistry , physics , organic chemistry , quantum mechanics , politics , political science , law
Given the tremendous potential applications of excited state intramolecular proton transfer (ESIPT) systems, ESIPT molecules have received widespread attention. In this work, based on density functional theory (DFT) and time‐dependent DFT (TDDFT) methods, we theoretically study the excited state dynamical behaviors of salicyladazine (SA) molecules. Our simulated results show that the double intramolecular hydrogen bonds of SA are strengthened in the S 1 state via exploring bond distances, bond angles, and infrared (IR) vibrational spectra. Exploring the frontier molecular orbitals (MOs), we confirm that charge redistributions indeed have effects on excited state dynamical behaviors. The increased electronic densities on N atoms and the decreased electronic densities on O atoms imply that charge redistribution may trigger the ESPT process. Analyzing the constructed S 0 ‐state and S 1 ‐state potential energy surfaces (PESs), we confirm that only the excited state single proton transfer reaction can occur although SA possesses two intramolecular hydrogen bonds. In this work, we clarify the specific ESIPT mechanism, which may facilitate developing novel applications based on the SA system in future.