Time‐dependent density functional theory study on excited‐state dihydrogen bonding OH···HGe of the dihydrogen‐bonded phenol‐triethylgermanium complex

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.