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

Liu，Qian1; Li，Zheng1; Liu，Peng1; Yang，Xueming1,2,3; Yu，Shengrui1

2023-05-07

10.1063/5.0150850

Journal of Chemical Physics   影响因子和分区

0021-9606

1089-7690

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(XΣ) + O(P) channels following excitation to the 2Σ(ν′,1,0) state has not been clearly understood so far. Here, we investigate the O(P) 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(Σ). The fitted CS(Σ) vibrational state distributions differ for the three P 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(Σ, v). The CS(XΣ, v = 0) has a significantly strong population at several shorter wavelengths, and the most populated CS(XΣ, v) is gradually transferred to a higher vibrational state with the decrease in the photolysis wavelength. The measured overall β-values for the three P 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(Σ) vibrational excitation at all studied photolysis wavelengths. The comparison of the experimental observations for this titled channel and the S(P) channel reveals that two different intersystem crossing mechanisms may be involved in the formation of the CS(XΣ) + O(P) photoproducts via the 2Σ state.

SCI ; EI

英语

其他

National Natural Science Foundation of China["22173082","21773213"] ; Zhejiang Provincial Natural Science Foundation of China[LY22B030005]

Chemistry ; Physics

Chemistry, Physical ; Physics, Atomic, Molecular & Chemical

WOS:001010624200003

AIP Publishing

20231914077330

Atmospheric chemistry ; Excited states ; Kinetic energy ; Kinetics ; Sulfur compounds

Atmospheric Properties:443.1 ; Fluid Flow, General:631.1 ; Chemistry, General:801.1 ; Physical Chemistry:801.4 ; Classical Physics; Quantum Theory; Relativity:931 ; Atomic and Molecular Physics:931.3 ; Quantum Theory; Quantum Mechanics:931.4

CHEMISTRY

2-s2.0-85158059320

Scopus

1.Hangzhou Institute of Advanced Studies,Zhejiang Normal University,Hangzhou,1108 Gengwen Road Zhejiang Province,311231,China
2.State Key Laboratory of Molecular Reaction Dynamics and Dalian Coherent Light Source,Dalian Institute of Chemical Physics,Chinese Academy of Sciences,Liaoning,457 Zhongshan Road, Dalian,116023,China
3.Department of Chemistry,College of Science,Southern University of Science and Technology,Shenzhen,518055,China

Liu，Qian,Li，Zheng,Liu，Peng,et al. Resonance-state selective photodissociation dynamics of OCS + hv → CS(X1Σ+) + O(3Pj=2,1,0) via the 21Σ+ state[J]. Journal of Chemical Physics,2023,158(17).

Liu，Qian,Li，Zheng,Liu，Peng,Yang，Xueming,&Yu，Shengrui.(2023).Resonance-state selective photodissociation dynamics of OCS + hv → CS(X1Σ+) + O(3Pj=2,1,0) via the 21Σ+ state.Journal of Chemical Physics,158(17).

Liu，Qian,et al."Resonance-state selective photodissociation dynamics of OCS + hv → CS(X1Σ+) + O(3Pj=2,1,0) via the 21Σ+ state".Journal of Chemical Physics 158.17(2023).