Time-dependent density functional theory study on excited-state dihydrogen bonding OH···HGe of the dihydrogen-bonded phenol-triethylgermanium complex

✍ Scribed by Ning-Ning Wei; Ce Hao; Zhilong Xiu; Jingwen Chen; Jieshan Qiu

• Publisher: John Wiley and Sons
• Year: 2010
• Tongue: English
• Weight: 471 KB
• Volume: 31
• Category: Article
• ISSN: 0192-8651
• DOI: 10.1002/jcc.21579

✦ Synopsis

Abstract

Intermolecular dihydrogen bond OH···HGe in the electronically excited state of the dihydrogen‐bonded phenol–triethylgermanium (TEGH) 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···H distance significantly decreases in the S~1~ state. Thus, the intermolecular dihydrogen bond OH···HGe of the dihydrogen‐bonded phenol–TEGH complex becomes stronger in the electronically excited state than that in the ground state. © 2010 Wiley Periodicals, Inc. J Comput Chem 2010