Title: Direct observation of ring-opening dynamics in strong-field ionized selenophene using femtosecond inner-shell absorption spectroscopy

Abstract

Femtosecond extreme ultraviolet transient absorption spectroscopy is used to explore strong-field ionization induced dynamics in selenophene (C₄H₄Se). The dynamics are monitored in real-time from the viewpoint of the Se atom by recording the temporal evolution of element-specific spectral features near the Se 3d inner-shell absorption edge (~58 eV). The interpretation of the experimental results is supported by first-principles time-dependent density functional theory calculations. The experiments simultaneously capture the instantaneous population of stable molecular ions, the emergence and decay of excited cation states, and the appearance of atomic fragments. The experiments reveal, in particular, insight into the strong-field induced ring-opening dynamics in the selenophene cation, which are traced by the emergence of non-cyclic molecules as well as the liberation of Se + ions within an overall time scale of approximately 170 fs. In this study, we propose that both products may be associated with dynamics on the same electronic surfaces but with different degrees of vibrational excitation. The time-dependent inner-shell absorption features provide direct evidence for a complex relaxation mechanism that may be approximated by a two-step model, whereby the initially prepared, excited cyclic cation decays within τ₁ = 80 ± 30 fs into a transient molecular species, which then givesmore » rise to the emergence of bare Se + and ring-open cations within an additional τ₂ = 80 ± 30 fs. The combined experimental and theoretical results suggest a close relationship between σ* excited cation states and the observed ring-opening reactions. In conclusion, the findings demonstrate that the combination of femtosecond time-resolved core-level spectroscopy with ab initio estimates of spectroscopic signatures provide new insights into complex, ultrafast photochemical reactions such as ring-opening dynamics in organic molecules in real-time and with simultaneous sensitivity for electronic and structural rearrangements.« less

Authors:

Lackner, Florian  ^[1];

• Search DOE PAGES for author "Lackner, Florian"
• Search DOE PAGES for ORCID "0000-0003-3047-5659"

Chatterley, Adam S.  ^[1];

• Search DOE PAGES for author "Chatterley, Adam S."
• Search DOE PAGES for ORCID "0000-0003-3847-5936"

Pemmaraju, C. D. ^[2]; Closser, Kristina D. ^[3]; Prendergast, David ^[4]; Neumark, Daniel M.  ^[1];

• Search DOE PAGES for author "Neumark, Daniel M."
• Search DOE PAGES for ORCID "0000-0002-3762-9473"

Leone, Stephen R. ^[5]; Gessner, Oliver  ^[6]

• Search DOE PAGES for author "Gessner, Oliver"
• Search DOE PAGES for ORCID "0000-0003-4709-2822"

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+ Show Author Affiliations

1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Department of Chemistry
2. Chemical Sciences Division, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA; The Molecular Foundry, Lawrence Berkeley National Laboratory, Berkeley, California 94720, USA
3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division and The Molecular Foundry
4. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). The Molecular Foundry
5. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Department of Chemistry and Department of Physics
6. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division

Publication Date:

Wed Dec 21 00:00:00 EST 2016

Research Org.:

Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)

Sponsoring Org.:

SC-22.1 USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE

OSTI Identifier:

1439210

Alternate Identifier(s):

OSTI ID: 1364068

Grant/Contract Number:  

AC02-05CH11231

Resource Type:

Accepted Manuscript

Journal Name:

Journal of Chemical Physics

Additional Journal Information:

Journal Volume: 145; Journal Issue: 23; Related Information: © 2016 Author(s).; Journal ID: ISSN 0021-9606

Publisher:

American Institute of Physics (AIP)

Country of Publication:

United States

Language:

English

Subject:

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY