Direct observation of the solvent reorientation dynamics in the “twisted” intramolecular charge-transfer process of cyanophenyldisilane–water cluster by transient infrared spectroscopy

Abstract

The solvent reorientation dynamics of the intramolecular charge-transfer (ICT) process of the (p-cyanophenyl)pentamethyldisilane-H(2)O (CPDS-H(2)O) cluster was investigated by transient infrared (IR) absorption spectroscopy. Transient IR bands of two distinct charge-transfer (CT) states appeared in both the OH and the CN-stretching vibration regions. Analyses of the IR spectra and the time profiles of the transient bands revealed that the ICT process of the CPDS-H(2)O cluster proceeds in two steps. The first step is a transition from a photo-prepared locally excited (LE) state to the CT state, which is accompanied by a minor reorientation of the H(2)O moiety. In contrast, the second step is an extensive reorientation process of the H(2)O molecule in the CT state. These two reorientation processes exhibit very distinct pico- and nano-second time scales. In the latter case, a relatively slow time constant of 2 ns was related to a large geometric change in the orientation.