title: Novel infrared spectra for intermolecular dihydrogen bonding of the phenol-borane-trimethylamine complex in electronically excited state.
abstract: The intermolecular dihydrogen bonding in the electronically excited states of the dihydrogen-bonded phenol-BTMA complex in gas phase was theoretically investigated using the time-dependent density functional theory method for the first time. It was theoretically demonstrated that the S(1) state of the dihydrogen-bonded phenol-BTMA complex is a locally excited state, in which only the phenol moiety is electronically excited. The infrared spectra of the dihydrogen-bonded phenol-BTMA complex in ground state and the S(1) state were calculated at both the O-H and B-H stretching vibrational regions. A novel infrared spectrum of the dihydrogen-bonded phenol-BTMA complex in the electronically excited state was found. The stretching vibrational absorption bands of the dihydrogen-bonded O-H and B-H groups are very strong in the ground state, while they are disappeared in the S(1) state. At the same time, a new strong absorption band appears at the C[Double Bond]O stretching region. From the calculated bond lengths, it was found that both the O-H and B-H bonds in the dihydrogen bond O-H...H-B are significantly lengthened in the S(1) state of the dihydrogen-bonded phenol-BTMA complex. However, the C-O bond in the phenol moiety is markedly shortened in the excited state, and then has the characteristics of C[Double Bond]O group. Furthermore, it was demonstrated that the intermolecular dihydrogen bonds in the electronically excited state of the dihydrogen-bonded phenol-BTMA complex are strengthened, since calculated H...H distance is drastically shortened in the S(1) state.
authors.affiliation: State Key Laboratory of Molecular Reaction Dynamics, Dalian Institute of Chemical Physics, Chinese Academy of Sciences, Dalian 116023, Liaoning, China.
authors.forename: Guang-Jiu
authors.initials: GJ
authors.lastname: Zhao
authors.forename: Ke-Li
authors.initials: KL
authors.lastname: Han
mesh_terms: D000042:Absorption; D001880:Boranes / Q000737:chemistry*; D002627:Chemistry, Physical / Q000379:methods; D004581:Electronics; D006860:Hydrogen Bonding; D008744:Methylamines / Q000737:chemistry*; D008962:Models, Theoretical; D008968:Molecular Conformation; D019800:Phenol / Q000737:chemistry*; D013055:Spectrophotometry, Infrared / Q000379:methods*
chemical_list: D001880:Boranes; D008744:Methylamines; D019800:Phenol; C023336:trimethylamine