Resonance-state selective photodissociation dynamics of OCS + hv → CS(X1Σ+) + O(3Pj=2,1,0) via the 21Σ+ state

Abstract

Understanding vacuum ultraviolet photodissociation dynamics of Carbonyl sulfide (OCS) is of considerable importance in the study of atmospheric chemistry. Yet, photodissociation dynamics of the CS(X1Σ+) + O(3Pj=2,1,0) channels following excitation to the 21Σ+(ν1′,1,0) state has not been clearly understood so far. Here, we investigate the O(3Pj=2,1,0) elimination dissociation processes in the resonance-state selective photodissociation of OCS between 147.24 and 156.48 nm by using the time-sliced velocity-mapped ion imaging technique. The total kinetic energy release spectra are found to exhibit highly structured profiles, indicative of the formation of a broad range of vibrational states of CS(1Σ+). The fitted CS(1Σ+) vibrational state distributions differ for the three 3Pj spin–orbit states, but a general trend of the inverted characteristics is observed. Additionally, the wavelength-dependent behaviors are also observed in the vibrational populations for CS(1Σ+, v). The CS(X1Σ+, v = 0) has a significantly strong population at several shorter wavelengths, and the most populated CS(X1Σ+, v) is gradually transferred to a higher vibrational state with the decrease in the photolysis wavelength. The measured overall β-values for the three 3Pj spin–orbit channels slightly increase and then abruptly decrease as the photolysis wavelength increases, while the vibrational dependences of β-values show an irregularly decreasing trend with increasing CS(1Σ+) vibrational excitation at all studied photolysis wavelengths. The comparison of the experimental observations for this titled channel and the S(3Pj) channel reveals that two different intersystem crossing mechanisms may be involved in the formation of the CS(X1Σ+) + O(3Pj=2,1,0) photoproducts via the 21Σ+ state.

Wavelength-Dependent Dynamics of the O(1D2) Channel in the 1Δu State Photodissociation of CO2

“…The experiment employed the time-sliced velocity-mapped ion imaging apparatus combined with two independent laser sources (a tunable VUV source for photolysis and a fixed UV source for (2 + 1) REMPI detection) for CO 2 molecular photodissociation. The detailed configuration of the experimental setup has been introduced in our previous studies, − and thus only a brief description is presented here. The CO 2 molecular beam (the rotational temperature was ∼10 K) was formed in a pulsed supersonic expansion of 10% CO 2 in Ar at a 1 bar backing pressure.…”