Attosecond XUV probing of vibronic quantum superpositions in Br2+
Abstract
Ultrafast laser excitation can create coherent superpositions of electronic states in molecules and trigger ultrafast flow of electron density on a few femtosecond timescale. While recent attosecond experiments have addressed real-time observation of these primary photochemical processes, the underlying roles of simultaneous nuclear motions and how they modify and disturb the valence electronic motion remain uncertain. In this work, we investigate coherent electronic-vibrational dynamics induced among multiple vibronic levels of ionic bromine (Br2+), including both spin-orbit (X2Π3/2,g – X2Π1/2,g) and valence (A2Π3/2,u – 4Σ3/2,u) electronic superpositions, using attosecond transient absorption spectroscopy. Decay, revival, and apparent frequency shifts of electronic coherences are measured via characteristic quantum beats on the Br-3d core-level absorption signals. Quantum-mechanical simulations attribute the observed electronic decoherence to broadened phase distributions of nuclear wave packets on anharmonic potentials. Molecular vibronic structure is further revealed to be imprinted as discrete progressions in electronic beat frequencies. These results provide a future basis to interpret complex charge-migration dynamics in polyatomic systems.
- Authors:
-
[1];
[2];
[2]
- Univ. of California, Berkeley, CA (United States)
- Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC); National Science Foundation (NSF); US Army Research Office (ARO)
- OSTI Identifier:
- 1762196
- Grant/Contract Number:
- AC02-05CH11231; CHE-1660417; CHE-1951317; W911NF-14-1-0383; W911NF-20-1-0127
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review A
- Additional Journal Information:
- Journal Volume: 102; Journal Issue: 5; Journal ID: ISSN 2469-9926
- Publisher:
- American Physical Society (APS)
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 74 ATOMIC AND MOLECULAR PHYSICS
Citation Formats
Kobayashi, Yuki, Neumark, Daniel M., and Leone, Stephen R. Attosecond XUV probing of vibronic quantum superpositions in Br2+. United States: N. p., 2020.
Web. doi:10.1103/physreva.102.051102.
Kobayashi, Yuki, Neumark, Daniel M., & Leone, Stephen R. Attosecond XUV probing of vibronic quantum superpositions in Br2+. United States. https://doi.org/10.1103/physreva.102.051102
Kobayashi, Yuki, Neumark, Daniel M., and Leone, Stephen R. Fri .
"Attosecond XUV probing of vibronic quantum superpositions in Br2+". United States. https://doi.org/10.1103/physreva.102.051102. https://www.osti.gov/servlets/purl/1762196.
@article{osti_1762196,
title = {Attosecond XUV probing of vibronic quantum superpositions in Br2+},
author = {Kobayashi, Yuki and Neumark, Daniel M. and Leone, Stephen R.},
abstractNote = {Ultrafast laser excitation can create coherent superpositions of electronic states in molecules and trigger ultrafast flow of electron density on a few femtosecond timescale. While recent attosecond experiments have addressed real-time observation of these primary photochemical processes, the underlying roles of simultaneous nuclear motions and how they modify and disturb the valence electronic motion remain uncertain. In this work, we investigate coherent electronic-vibrational dynamics induced among multiple vibronic levels of ionic bromine (Br2+), including both spin-orbit (X2Π3/2,g – X2Π1/2,g) and valence (A2Π3/2,u – 4Σ3/2,u) electronic superpositions, using attosecond transient absorption spectroscopy. Decay, revival, and apparent frequency shifts of electronic coherences are measured via characteristic quantum beats on the Br-3d core-level absorption signals. Quantum-mechanical simulations attribute the observed electronic decoherence to broadened phase distributions of nuclear wave packets on anharmonic potentials. Molecular vibronic structure is further revealed to be imprinted as discrete progressions in electronic beat frequencies. These results provide a future basis to interpret complex charge-migration dynamics in polyatomic systems.},
doi = {10.1103/physreva.102.051102},
journal = {Physical Review A},
number = 5,
volume = 102,
place = {United States},
year = {Fri Nov 13 00:00:00 EST 2020},
month = {Fri Nov 13 00:00:00 EST 2020}
}
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