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Transient vibration and product formation of photoexcited CS<inf>2</inf>measured by time-resolved X-ray scattering
Journal
Journal of Chemical Physics
ISSN
00219606
Date Issued
2022-10-28
Author(s)
Gabalski, Ian
Sere, Malick
Acheson, Kyle
Allum, Felix
Boutet, Sébastien
Dixit, Gopal
Forbes, Ruaridh
Glownia, James M.
Goff, Nathan
Hegazy, Kareem
Howard, Andrew J.
Liang, Mengning
Minitti, Michael P.
Minns, Russell S.
Natan, Adi
Peard, Nolan
Rasmus, Weronika O.
Sension, Roseanne J.
Ware, Matthew R.
Weber, Peter M.
Werby, Nicholas
Wolf, Thomas J.A.
Kirrander, Adam
Bucksbaum, Philip H.
Abstract
We have observed details of the internal motion and dissociation channels in photoexcited carbon disulfide (CS2) using time-resolved X-ray scattering (TRXS). Photoexcitation of gas-phase CS2 with a 200 nm laser pulse launches oscillatory bending and stretching motion, leading to dissociation of atomic sulfur in under a picosecond. During the first 300 fs following excitation, we observe significant changes in the vibrational frequency as well as some dissociation of the C-S bond, leading to atomic sulfur in the both 1D and 3P states. Beyond 1400 fs, the dissociation is consistent with primarily 3P atomic sulfur dissociation. This channel-resolved measurement of the dissociation time is based on our analysis of the time-windowed dissociation radial velocity distribution, which is measured using the temporal Fourier transform of the TRXS data aided by a Hough transform that extracts the slopes of linear features in an image. The relative strength of the two dissociation channels reflects both their branching ratio and differences in the spread of their dissociation times. Measuring the time-resolved dissociation radial velocity distribution aids the resolution of discrepancies between models for dissociation proposed by prior photoelectron spectroscopy work.
Volume
157
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