Issue 44, 2022

Two-photon dissociation dynamics of the mercapto radical

Abstract

Two-photon dissociation dynamics of the SH/SD radicals are investigated using the high-n Rydberg atom time-of-flight (HRTOF) technique. The H/D(2S) + S(1D) and H/D(2S) + S(1S) products are observed in the dissociation of the SH/SD radicals on the 22Π and B2Σ+ repulsive states, from sequential two-photon excitation via the A2Σ+ (v′ = 0, J′ = 0.5–2.5) state. The angular distributions of both H/D(2S) + S(1D) and H/D(2S) + S(1S) product channels are anisotropic. The anisotropy parameter (β) of the H(2S) + S(1D) products is ∼−0.8 ± 0.1 (−0.9 ± 0.05 for SD), and that of the H(2S) + S(1S) products is ∼1.3 ± 0.3 (1.2 for SD). The anisotropic angular distributions indicate that the SH/SD radicals promptly dissociate on the repulsive 22Π and B2Σ+ potential energy curves (PECs) along with some non-adiabatic crossings, leading to the H/D(2S) + S(1D) and H/D(2S) + S(1S) products, respectively. The bond dissociation energy of the ground-state X2Π3/2 SH/SD to the ground-state H/D(2S) + S(3P2) products is measured to be D0(S–H) = 29 253 ± 20 cm−1 and D0(S–D) = 29 650 ± 20 cm−1, respectively. The dissociation energy of the A2Σ+ state SH/SD to the H/D(2S) + S(1D) products is derived to be D0[S–H(A)] = 7659 ± 20 cm−1 and D0[S–D(A)] = 7940 ± 20 cm−1.

Graphical abstract: Two-photon dissociation dynamics of the mercapto radical

Article information

Article type
Paper
Submitted
04 Sep 2022
Accepted
13 Oct 2022
First published
13 Oct 2022

Phys. Chem. Chem. Phys., 2022,24, 27232-27240

Author version available

Two-photon dissociation dynamics of the mercapto radical

Y. Qin, X. Zheng, Y. Song, G. Sun and J. Zhang, Phys. Chem. Chem. Phys., 2022, 24, 27232 DOI: 10.1039/D2CP04116B

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