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TDDFT study on the excited‐state hydrogen bonding of N‐(2‐hydroxyethyl)‐1,8‐naphthalimide and N‐(3‐hydroxyethyl)‐1,8‐naphthalimide in methanol solution
Author(s) -
Li Hui,
Yang Yonggang,
Yang Dapeng,
Liu Yufang,
Sun Jinfeng
Publication year - 2014
Publication title -
journal of physical organic chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.325
H-Index - 66
eISSN - 1099-1395
pISSN - 0894-3230
DOI - 10.1002/poc.3255
Subject(s) - time dependent density functional theory , chemistry , excited state , density functional theory , intramolecular force , hydrogen bond , intermolecular force , monomer , molecule , photochemistry , computational chemistry , atomic physics , stereochemistry , organic chemistry , polymer , physics
The time‐dependent density functional theory method was performed to investigate the excited‐state hydrogen‐bonding dynamics of N‐(2‐hydroxyethyl)‐1,8‐naphthalimide (2a) and N‐(3‐hydroxyethyl)‐1,8‐naphthalimide (3a) in methanol (meoh) solution. The ground and excited‐state geometry optimizations, electronic excitation energies, and corresponding oscillation strengths of the low‐lying electronically excited states for the complexes 2a + 2meoh and 3a + 2meoh as well as their monomers 2a and 3a were calculated by density functional theory and time‐dependent density functional theory methods, respectively. We demonstrated that the three intermolecular hydrogen bonds of 2a + 2meoh and 3a + 2meoh are strengthened after excitation to the S 1 state, and thus induce electronic spectral redshift. Moreover, the electronic excitation energies of the hydrogen‐bonded complexes in S 1 state are correspondingly decreased compared with those of their corresponding monomer 2a and 3a. In addition, the intramolecular charge transfer of the S 1 state for complexes 2a + 2meoh and 3a + 2meoh were theoretically investigated by analysis of molecular orbital. Copyright © 2014 John Wiley & Sons, Ltd.