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Time‐dependent density functional theory study on the electronic excited‐state hydrogen‐bonding dynamics of 4‐aminophthalimide (4AP) in aqueous solution: 4AP and 4AP–(H 2 O) 1,2 clusters
Author(s) -
Wang Rui,
Hao Ce,
Li Peng,
Wei NingNing,
Chen Jingwen,
Qiu Jieshan
Publication year - 2010
Publication title -
journal of computational chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.907
H-Index - 188
eISSN - 1096-987X
pISSN - 0192-8651
DOI - 10.1002/jcc.21504
Subject(s) - hydrogen bond , excited state , time dependent density functional theory , chemistry , density functional theory , intermolecular force , photochemistry , hydrogen , computational chemistry , molecule , crystallography , atomic physics , organic chemistry , physics
The time‐dependent density functional theory (TDDFT) method has been carried out to investigate the excited‐state hydrogen‐bonding dynamics of 4‐aminophthalimide (4AP) in hydrogen‐donating water solvent. The infrared spectra of the hydrogen‐bonded solute−solvent complexes in electronically excited state have been calculated using the TDDFT method. We have demonstrated that the intermolecular hydrogen bond C O···HO and NH···OH in the hydrogen‐bonded 4AP−(H 2 O) 2 trimer are significantly strengthened in the electronically excited state by theoretically monitoring the changes of the bond lengths of hydrogen bonds and hydrogen‐bonding groups in different electronic states. The hydrogen bonds strengthening in the electronically excited state are confirmed because the calculated stretching vibrational modes of the hydrogen bonding CO, amino NH, and HO groups are markedly red‐shifted upon photoexcitation. The calculated results are consistent with the mechanism of the hydrogen bond strengthening in the electronically excited state, while contrast with mechanism of hydrogen bond cleavage. Furthermore, we believe that the transient hydrogen bond strengthening behavior in electroniclly excited state of chromophores in hydrogen‐donating solvents exists in many other systems in solution. © 2010 Wiley Periodicals, Inc. J Comput Chem, 2010