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

Literature Information

Publication Date 2006-11-17
DOI 10.1039/B612758D
Impact Factor 3.676
Authors

Haruki Ishikawa, Masuyuki Sugiyama, Wataru Setaka, Mitsuo Kira, Naohiko Mikami


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Abstract

The solvent reorientation dynamics of the intramolecular charge-transfer (ICT) process of the (p-cyanophenyl)pentamethyldisilane–H2O (CPDS–H2O) 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–H2O 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 H2O moiety. In contrast, the second step is an extensive reorientation process of the H2O 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.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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