Unmasking the cis-stilbene phantom state via vacuum ultraviolet time-resolved photoelectron spectroscopy and Ab initio multiple spawning

DOI	Resolve DOI: https://doi.org/10.1021/acs.jpclett.1c01227
Author	Search for: Williams, Monika ORCID identifier: https://orcid.org/0000-0003-2292-6501; Search for: Forbes, Ruaridh ORCID identifier: https://orcid.org/0000-0003-2097-5991; Search for: Weir, Hayley ORCID identifier: https://orcid.org/0000-0002-1039-327X; Search for: Veyrinas, Kévin; Search for: MaCdonell, Ryan J.¹; Search for: Boguslavskiy, Andrey E.¹; Search for: Schuurman, Michael S.¹ORCID identifier: https://orcid.org/0000-0002-0922-9034; Search for: Stolow, Albert¹ORCID identifier: https://orcid.org/0000-0002-8447-3678; Search for: Martinez, Todd J.ORCID identifier: https://orcid.org/0000-0002-4798-8947
Affiliation	National Research Council Canada. Security and Disruptive Technologies
Format	Text, Article
Subject	ionization; photoionization; energy; quantum mechanics; probes
Abstract	We present the first vacuum ultraviolet time-resolved photoelectron spectroscopy (VUV-TRPES) study of photoisomerization dynamics in the paradigmatic molecule cis-stilbene. A key reaction intermediate in its dynamics, known as the phantom state, has often been invoked but never directly detected in the gas phase. We report direct spectral signatures of the phantom state in isolated cis-stilbene, observed and characterized through a combination of VUV-TRPES and ab initio multiple spawning (AIMS) nonadiabatic dynamics simulations of the channel-resolved observable. The high VUV probe photon energy tracks the complete excited-state dynamics via multiple photoionization channels, from initial excitation to its return to the “hot” ground state. The TRPES was compared with AIMS simulations of the dynamics from initial excitation, to the phantom-state intermediate (an S1 minimum), through to the ultimate electronic decay to the ground state. This combination revealed the unique spectral signatures and time-dependent dynamics of the phantom-state intermediate, permitting us to report here its direct observation.
Publication date	2021-07-07
Publisher	American Chemical Society
In	The Journal of Physical Chemistry Letters 12, no. 27 (7 July 2021): 6363–6369.
Language	English
Peer reviewed	Yes
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Record identifier	07887402-544f-44e0-8a89-9d6fde74f04a
Record created	2022-02-04
Record modified	2022-02-04

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