Time-resolved X-ray photoelectron spectroscopy: ultrafast dynamics in CS2 probed at the S 2p edge

Time-resolved X-ray photoelectron spectroscopy: ultrafast dynamics in CS2 probed at the S 2p edge

Recent developments in X-ray free-electron lasers have enabled a novel site-selective probe of coupled nuclear and electronic dynamics in photoexcited molecules, time-resolved X-ray photoelectron spectroscopy (TRXPS). We present results from a joint experimental and theoretical TRXPS study of the we...

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Bibliographic Details
Main Authors: Gabalski, I, Allum, F, Seidu, I, Britton, M, Brenner, G, Bromberger, H, Brouard, M, Bucksbaum, PH, Burt, M, Cryan, JP, Driver, T, Ekanayake, N, Erk, B, Garg, D, Gougoula, E, Heathcote, D, Hockett, P, Holland, DMP, Howard, AJ, Kumar, S, Lee, JWL, Li, S, McManus, J, Mikosch, J, Milesevic, D, Minns, RS, Neville, S, Atia-Tul-Noor, Papadopoulou, CC, Passow, C, Razmus, WO, Röder, A, Rouzée, A, Simao, A, Unwin, J, Vallance, C, Walmsley, T, Wang, J, Rolles, D, Stolow, A, Schuurman, MS, Forbes, R
Format: Journal article
Language:English
Published: American Chemical Society 2023
Subjects:
Photodissociation
Dissociation
Sulfur
Ionization
Ultrafast phenomena
Description
Summary:Recent developments in X-ray free-electron lasers have enabled a novel site-selective probe of coupled nuclear and electronic dynamics in photoexcited molecules, time-resolved X-ray photoelectron spectroscopy (TRXPS). We present results from a joint experimental and theoretical TRXPS study of the well-characterized ultraviolet photodissociation of CS<sub>2</sub>, a prototypical system for understanding non-adiabatic dynamics. These results demonstrate that the sulfur 2p binding energy is sensitive to changes in the nuclear structure following photoexcitation, which ultimately leads to dissociation into CS and S photoproducts. We are able to assign the main X-ray spectroscopic features to the CS and S products via comparison to a first-principles determination of the TRXPS based on <i>ab initio</i> multiple-spawning simulations. Our results demonstrate the use of TRXPS as a local probe of complex ultrafast photodissociation dynamics involving multimodal vibrational coupling, nonradiative transitions between electronic states, and multiple final product channels.

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