Release Time:2019-03-09  Hits:

Indexed by: Journal Article

Date of Publication: 2010-12-01

Journal: JOURNAL OF COMPUTATIONAL CHEMISTRY

Included Journals: SCIE

Volume: 31

Issue: 16

Page Number: 2853-2858

ISSN: 0192-8651

Key Words: dihydrogen bonding; time-dependent density functional theory; electronically excited state; infrared spectra

Abstract: Intermolecular dihydrogen bond O-H center dot center dot center dot H-Ge in the electronically excited state of the dihydrogen-bonded phenol-triethylgermanium (TECH) complex was studied theoretically using time-dependent density functional theory. Analysis of the frontier molecular orbitals revealed a locally excited S(1) state in which only the phenol moiety is electronically excited. In the predicted infrared spectrum of the dihydrogen-bonded phenol-TEGH complex, the O-H stretching vibrational mode shifts to a lower frequency in the S(1) state in comparison with that in ground state. The Ge-H stretching vibrational mode demonstrates a relatively smaller redshift than the O-H stretching vibrational mode. Upon electronic excitation to the S(1) state, the O-H and Ge-H bonds involved in the dihydrogen bond both get lengthened, whereas the C-O bond is shortened. With an increased binding energy, the calculated H center dot center dot center dot H distance significantly decreases in the S(1) state. Thus, the intermolecular dihydrogen bond O-H center dot center dot center dot H-Ge of the dihydrogen-bonded phenol-TEGH complex becomes stronger in the electronically excited state than that in the ground state. (C) 2010 Wiley Periodicals, Inc. J Comput Chem 31: 2853-2858, 2010