(1+1) Resonance‐Enhanced Multiphoton Ionization and Photodissociation Study of CS2 via the 1B2 State

Abstract

(1+1) Resonance-enhanced multiphoton ionization (REMPI) spectra of CS(2) and molecular dissociation dynamics are investigated using a time-of-flight mass spectrometer equipped with velocity imaging detection. The REMPI spectra via a linear-bent 1Sigma(g)+-->(1)B(2)(1Sigma(u)+) transition are acquired in the wavelength range of 208-217 nm. Each ro-vibrational band profile of the (1)B(2)(1Sigma(u)+) state is deconvoluted to yield the corresponding predissociative lifetime from 0.3 to 3 ps. Upon excitation at 210.25 and 212.54 nm, the resulting images of S(+) and CS(+) fragments are analyzed to give individual translational energy distributions, which are resolved into two components corresponding to the CS+S((3)P) and CS+S((1)D) channels. The product branching ratios of S((3)P)/S((1)D) are evaluated to be 5.7+/-1.0 and 9.6+/-2.5 at 210.25 and 212.54 nm, respectively. Despite the difficulty avoiding the effect of multiphoton absorption, the molecular dissociation channel is verified to prevail over the dissociative ionization channel of CS(2). The anisotropy parameters for the triplet and singlet channels are determined to be approximately 0.8 and 1.1-1.3, respectively, suggesting that the predissociative state should have a bent configuration with a short lifetime.