Intracluster Ion−Molecule Reactions of Phenylsilane Dimer Cation following the Charge Resonance Band Excitation

Abstract

Photoinitiated intracluster ion−molecule reactions of phenylsilane dimer cation have been investigated for the first time. The reaction products were the same as those reported in the gas-phase study. The photodepletion spectrum of the parent dimer ion and the action spectra of the reaction products were observed in the region of 6000−22 000 cm-1. All the spectra exhibit an intense band appearing in near-IR region, which is associated with the charge resonance (CR) transition of the dimer ion. It was found that the intracluster reactions are preferential for an isomer of the dimer cation having a parallel conformation of two phenyl rings which exhibits the CR transition.

Intracluster Ion−Molecule Reactions of Dimer Cations of Phenylsilanes

“…. 3 The same ion-molecule reactions as those reported by the FT-ICR study 1 were observed in the photoexcitation of (PhSiH 3 ) 2 + in the region of 6000-22000 cm -1 . In addition, we have found that the intracluster reactions are preferential for an isomer of the dimer cation having a parallel conformation of two phenyl rings which exhibits the charge-resonance (CR) transition.…”

“…The RE2PI mass spectrum of (PhSiH 3 ) 2 in a skimmed molecular beam condition was also observed. As shown in Figure a of ref , ion signals of the reaction products were very weak. In the previous study, similar intracluster reactions were initiated by the photoexcitation at the CR band.…”

“…Phenylsilane, PhSiH 3 , is the simplest aromatic silicon compound. There are several reports on reactivities of its cationic species with neutral parent. − Nagano and others first investigated ion−molecule reactions of phenylsilane cation, , in gas phase by using Fourier transform ion cyclotron resonance (FT-ICR) method, and found the following reactions; …”

“…There are several reports on reactivities of its cationic species with neutral parent. [1][2][3][4] Nagano and others first investigated ion-molecule reactions of phenylsilane cation, PhSiH 3 + , in gas phase by using Fourier transform ion cyclotron resonance (FT-ICR) method, and found the following reactions; 1 Rate constants of the reactions 1a and 1b were determined to be 1.7 × 10 -10 and 3.2 × 10 -10 cm 3 molecule -1 s -1 , respectively. They also investigated the reaction of PhSiH 3 + with deuterated benzene, C 6 D 6 , and found that the following reaction takes place: while the reaction corresponding to reaction 1a does not take place.…”