biostudies-literatureUnknownWu YWe report time-sliced velocity map imaging studies of the methyl (CH<sub>3</sub>) and electronically excited sulfur (S(<sup>1</sup>D)) fragments formed following the photoexcitation of jet-cooled CH<sub>3</sub>SH molecules in the 2<sup>1</sup>A'' ← X̃ <sup>1</sup>A' absorption band (<i>i.e</i>. at wavelengths in the range 190 ≤ <i>λ</i> ≤ 210 nm). Analyses of images of CH<sub>3</sub> fragments in their <i>v</i> <sub>2</sub> = 0, 1 and 2 vibrational levels confirm the perpendicular parent transition dipole moment and prompt bond fission and show that the ground state SH(X) partners are formed with an inverted vibrational population distribution, peaking at <i>v</i> = 2 at the shortest excitation wavelengths investigated. Most of the photolysis photon energy above that required to break the Chemical sciencehttps://www.ebi.ac.uk/biostudies/studies/S-EPMC12396137biostudies-literatureUltraviolet photodissociation of methanethiol (CH<sub>3</sub>SH): revealing an S(<sup>1</sup>D) atom elimination channel.PMC12396137Yang XShuai QLi ZDong YLuo ZZhou SHua WYuan KDai DAshfold MNRYang SWu YfalseUltraviolet photodissociation of methanethiol (CH<sub>3</sub>SH): revealing an S(<sup>1</sup>D) atom elimination channel.We report time-sliced velocity map imaging studies of the methyl (CH<sub>3</sub>) and electronically excited sulfur (S(<sup>1</sup>D)) fragments formed following the photoexcitation of jet-cooled CH<sub>3</sub>SH molecules in the 2<sup>1</sup>A'' ← X̃ <sup>1</sup>A' absorption band (<i>i.e</i>. at wavelengths in the range 190 ≤ <i>λ</i> ≤ 210 nm). Analyses of images of CH<sub>3</sub> fragments in their <i>v</i> <sub>2</sub> = 0, 1 and 2 vibrational levels confirm the perpendicular parent transition dipole moment and prompt bond fission and show that the ground state SH(X) partners are formed with an inverted vibrational population distribution, peaking at <i>v</i> = 2 at the shortest excitation wavelengths investigated. Most of the photolysis photon energy above that required to break the 2025-01-01T00:00:00Z2025 Aug2026-05-29T15:09:18.507Z2026-04-08T05:07:07.195ZS-EPMC123961374089631910.1039/d5sc04716a