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Title: Disentangling conical intersection and coherent molecular dynamics in methyl bromide with attosecond transient absorption spectroscopy

Abstract

Attosecond probing of core-level electronic transitions provides a sensitive tool for studying valence molecular dynamics with atomic, state, and charge specificity. In this report, we employ attosecond transient absorption spectroscopy to follow the valence dynamics of strong-field initiated processes in methyl bromide. By probing the 3d core-to-valence transition, we resolve the strong field excitation and ensuing fragmentation of the neutral σ* excited states of methyl bromide. The results provide a clear signature of the non-adiabatic passage of the excited state wavepacket through a conical intersection. We additionally observe competing, strong field initiated processes arising in both the ground state and ionized molecule corresponding to vibrational and spin-orbit motion, respectively. The demonstrated ability to resolve simultaneous dynamics with few-femtosecond resolution presents a clear path forward in the implementation of attosecond XUV spectroscopy as a general tool for probing competing and complex molecular phenomena with unmatched temporal resolution.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [1];  [1];  [4];  [1]; ORCiD logo [2]; ORCiD logo [5];  [1]
  1. Univ. of California, Berkeley, CA (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Max Planck Inst. for the Structure and Dynamics of Matter, Hamburg (Germany); Peking Univ., Beijing (China)
  4. Univ. of Hamburg (Germany)
  5. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC); National Science Foundation (NSF); Army Research Office (ARO); USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1546796
Alternate Identifier(s):
OSTI ID: 1559236
Grant/Contract Number:  
AC02-76SF00515; W911NF-14-1-0383; CHE-1361226; CHE-1660417; AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Nature Communications
Additional Journal Information:
Journal Volume: 10; Journal Issue: 1; Journal ID: ISSN 2041-1723
Publisher:
Nature Publishing Group
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS

Citation Formats

Timmers, Henry, Zhu, Xiaolei, Li, Zheng, Kobayashi, Yuki, Sabbar, Mazyar, Hollstein, Maximilian, Reduzzi, Maurizio, Martínez, Todd J., Neumark, Daniel M., and Leone, Stephen R. Disentangling conical intersection and coherent molecular dynamics in methyl bromide with attosecond transient absorption spectroscopy. United States: N. p., 2019. Web. doi:10.1038/s41467-019-10789-7.
Timmers, Henry, Zhu, Xiaolei, Li, Zheng, Kobayashi, Yuki, Sabbar, Mazyar, Hollstein, Maximilian, Reduzzi, Maurizio, Martínez, Todd J., Neumark, Daniel M., & Leone, Stephen R. Disentangling conical intersection and coherent molecular dynamics in methyl bromide with attosecond transient absorption spectroscopy. United States. doi:10.1038/s41467-019-10789-7.
Timmers, Henry, Zhu, Xiaolei, Li, Zheng, Kobayashi, Yuki, Sabbar, Mazyar, Hollstein, Maximilian, Reduzzi, Maurizio, Martínez, Todd J., Neumark, Daniel M., and Leone, Stephen R. Tue . "Disentangling conical intersection and coherent molecular dynamics in methyl bromide with attosecond transient absorption spectroscopy". United States. doi:10.1038/s41467-019-10789-7. https://www.osti.gov/servlets/purl/1546796.
@article{osti_1546796,
title = {Disentangling conical intersection and coherent molecular dynamics in methyl bromide with attosecond transient absorption spectroscopy},
author = {Timmers, Henry and Zhu, Xiaolei and Li, Zheng and Kobayashi, Yuki and Sabbar, Mazyar and Hollstein, Maximilian and Reduzzi, Maurizio and Martínez, Todd J. and Neumark, Daniel M. and Leone, Stephen R.},
abstractNote = {Attosecond probing of core-level electronic transitions provides a sensitive tool for studying valence molecular dynamics with atomic, state, and charge specificity. In this report, we employ attosecond transient absorption spectroscopy to follow the valence dynamics of strong-field initiated processes in methyl bromide. By probing the 3d core-to-valence transition, we resolve the strong field excitation and ensuing fragmentation of the neutral σ* excited states of methyl bromide. The results provide a clear signature of the non-adiabatic passage of the excited state wavepacket through a conical intersection. We additionally observe competing, strong field initiated processes arising in both the ground state and ionized molecule corresponding to vibrational and spin-orbit motion, respectively. The demonstrated ability to resolve simultaneous dynamics with few-femtosecond resolution presents a clear path forward in the implementation of attosecond XUV spectroscopy as a general tool for probing competing and complex molecular phenomena with unmatched temporal resolution.},
doi = {10.1038/s41467-019-10789-7},
journal = {Nature Communications},
number = 1,
volume = 10,
place = {United States},
year = {2019},
month = {7}
}

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