title: New insights into the solvent-assisted excited-state double proton transfer of 2-(1H-pyrazol-5-yl)pyridine with alcoholic partners: a TDDFT investigation.
abstract: Excited-state double proton transfer (ESDPT) in the hydrogen-bonded 2-(1H-pyrazol-5-yl)pyridine with propyl alcoholic partner (PPP) was theoretically investigated by time-dependent density functional theory (TDDFT) method. Great changes have taken place for the calculated geometric structures, the electron density features and vibrational spectrum of PPP system in S0 and S1 state. Our results have demonstrated that ESDPT reaction happens within the system upon photoexcitation. We also found that the ESDPT process is facilitated by the electronically excited state intermolecular hydrogen bond strengthening. Particularly, after the photoexcitation from HOMO(π) to the LUMO(π(∗)), the rearrangement of electronic density distribution of frontier molecular orbitals (MOs) on pyridine and the pyrazol moieties exhibits a very important positive factor for the ESDPT. Furthermore, by the investigation of the stretching vibrations of NH and OH groups, the infrared (IR) spectroscopic results provide us not only a theoretical evidence of ESDPT, but also a considerable clue to characterize the nature of intermolecular reaction. In addition, efforts have also been devoted towards calculating the absorption peak, which shows good consistency with the experimental result of the studied system.
authors: Institute of Atomic and Molecular Physics, Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy, Jilin University, Changchun 130012, China.
authors: Hui
authors: H
authors: Li
authors: Institute of Atomic and Molecular Physics, Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy, Jilin University, Changchun 130012, China. Electronic address: shi_ying@jlu.edu.cn.
authors: Ying
authors: Y
authors: Shi
authors: Institute of Atomic and Molecular Physics, Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy, Jilin University, Changchun 130012, China.
authors: Hang
authors: H
authors: Yin
authors: Institute of Atomic and Molecular Physics, Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy, Jilin University, Changchun 130012, China.
authors: Ye
authors: Y
authors: Wang
authors: Institute of Atomic and Molecular Physics, Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy, Jilin University, Changchun 130012, China.
authors: Lin
authors: L
authors: Cong
authors: Institute of Atomic and Molecular Physics, Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy, Jilin University, Changchun 130012, China.
authors: Mingxing
authors: M
authors: Jin
authors: Institute of Atomic and Molecular Physics, Jilin Provincial Key Laboratory of Applied Atomic and Molecular Spectroscopy, Jilin University, Changchun 130012, China.
authors: Dajun
authors: D
authors: Ding
mesh_terms: D000438:Alcohols / Q000737:chemistry*; D004583:Electrons; D006860:Hydrogen Bonding; D008958:Models, Molecular; D008968:Molecular Conformation; D011522:Protons; D011720:Pyrazoles / Q000737:chemistry*; D011725:Pyridines / Q000737:chemistry*; D011789:Quantum Theory; D012995:Solubility; D013055:Spectrophotometry, Infrared
chemical_list: D000438:Alcohols; D011522:Protons; D011720:Pyrazoles; D011725:Pyridines; C023666:pyridine
keywords: Excited-state double proton transfer (ESDPT); Hydrogen bond; Infrared (IR) spectrum; TDDFT