Ab-initio surface hopping and multiphoton ionisation study of the photodissociation dynamics of CS2

[Display omitted] •Ab-initio quantum dynamics calculations of the excited state dynamics of CS2.•Multiphoton ionisation photoelectron spectroscopy measurements of CS2.•Vibrational motion and periodic population transfer lead to oscillations in the photoelectron spectrum.•Significant population trans...

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Bibliographic Details
Published in:Chemical physics letters 2017-09, Vol.683, p.383-388
Main Authors: Bellshaw, Darren, Horke, Daniel A., Smith, Adam D., Watts, Hannah M., Jager, Edward, Springate, Emma, Alexander, Oliver, Cacho, Cephise, Chapman, Richard T., Kirrander, Adam, Minns, Russell S.
Format: Article
Language:English
Subjects:
Non-adiabatic dynamics
Photodissociation
Photoelectron spectroscopy
Theoretical chemistry
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Summary:[Display omitted] •Ab-initio quantum dynamics calculations of the excited state dynamics of CS2.•Multiphoton ionisation photoelectron spectroscopy measurements of CS2.•Vibrational motion and periodic population transfer lead to oscillations in the photoelectron spectrum.•Significant population transfer into the triplet states observed within a few hundred femtoseconds. New ab initio surface hopping simulations of the excited state dynamics of CS2 including spin-orbit coupling are compared to new experimental measurements using a multiphoton ionisation probe in a photoelectron spectroscopy experiment. The calculations highlight the importance of the triplet states even in the very early time dynamics of the dissociation process and allow us to unravel the signatures in the experimental spectrum, linking the observed changes to both electronic and nuclear degrees of freedom within the molecule.
ISSN:0009-2614
1873-4448
DOI:10.1016/j.cplett.2017.02.058