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Title: Direct mapping of curve-crossing dynamics in IBr by attosecond transient absorption spectroscopy

Abstract

The electronic character of photoexcited molecules can abruptly change at avoided crossings and conical intersections. Here, we report direct mapping of the coupled interplay between electrons and nuclei in a prototype molecule, iodine monobromide (IBr), by using attosecond transient absorption spectroscopy. A few-femtosecond visible pulse resonantly excites the B ( Π 3 0+ ) , Y(0+), and Z(0+) states of IBr, and the photodissociation dynamics are tracked with an attosecond extreme-ultraviolet pulse that simultaneously probes the I-4dand Br-3dcore-level absorption edges. Direct comparison with quantum mechanical simulations unambiguously identifies the absorption features associated with adiabatic and diabatic channels at the B/Y avoided crossing and concurrent two-photon dissociation processes that involve the Y/Z avoided crossing. Finally, the results show clear evidence for rapid switching of valence-electronic character at the avoided crossing.

Authors:
ORCiD logo [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [3]
+ Show Author Affiliations
  1. Univ. of California, Berkeley, CA (United States)
  2. Carleton Univ., Ottawa, ON (Canada)
  3. Univ. of California, Berkeley, CA (United States); Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Publication Date:
Research Org.:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES); National Science Foundation (NSF); US Army Research Office (ARO); Natural Sciences and Engineering Research Council of Canada (NSERC); National Institutes of Health (NIH)
OSTI Identifier:
1580889
Grant/Contract Number:  
AC02-05CH11231; CHE-1660417; W911-NF-14-1-0383; RGPIN-2016-06276; S10OF023532
Resource Type:
Accepted Manuscript
Journal Name:
Science
Additional Journal Information:
Journal Volume: 365; Journal Issue: 6448; Journal ID: ISSN 0036-8075
Publisher:
AAAS
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Kobayashi, Yuki, Chang, Kristina F., Zeng, Tao, Neumark, Daniel M., and Leone, Stephen R. Direct mapping of curve-crossing dynamics in IBr by attosecond transient absorption spectroscopy. United States: N. p., 2019. Web. doi:10.1126/science.aax0076.
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Kobayashi, Yuki, Chang, Kristina F., Zeng, Tao, Neumark, Daniel M., & Leone, Stephen R. Direct mapping of curve-crossing dynamics in IBr by attosecond transient absorption spectroscopy. United States. https://doi.org/10.1126/science.aax0076
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Kobayashi, Yuki, Chang, Kristina F., Zeng, Tao, Neumark, Daniel M., and Leone, Stephen R. Fri . "Direct mapping of curve-crossing dynamics in IBr by attosecond transient absorption spectroscopy". United States. https://doi.org/10.1126/science.aax0076. https://www.osti.gov/servlets/purl/1580889.
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@article{osti_1580889,
title = {Direct mapping of curve-crossing dynamics in IBr by attosecond transient absorption spectroscopy},
author = {Kobayashi, Yuki and Chang, Kristina F. and Zeng, Tao and Neumark, Daniel M. and Leone, Stephen R.},
abstractNote = {The electronic character of photoexcited molecules can abruptly change at avoided crossings and conical intersections. Here, we report direct mapping of the coupled interplay between electrons and nuclei in a prototype molecule, iodine monobromide (IBr), by using attosecond transient absorption spectroscopy. A few-femtosecond visible pulse resonantly excites theB(Π30+), Y(0+), and Z(0+) states of IBr, and the photodissociation dynamics are tracked with an attosecond extreme-ultraviolet pulse that simultaneously probes the I-4dand Br-3dcore-level absorption edges. Direct comparison with quantum mechanical simulations unambiguously identifies the absorption features associated with adiabatic and diabatic channels at the B/Y avoided crossing and concurrent two-photon dissociation processes that involve the Y/Z avoided crossing. Finally, the results show clear evidence for rapid switching of valence-electronic character at the avoided crossing.},
doi = {10.1126/science.aax0076},
journal = {Science},
number = 6448,
volume = 365,
place = {United States},
year = {Fri Jul 05 00:00:00 EDT 2019},
month = {Fri Jul 05 00:00:00 EDT 2019}
}
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Journal Article:
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Publisher's Version of Record
https://doi.org/10.1126/science.aax0076
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Cited by: 66 works
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Figures / Tables:

Fig 1 Fig 1: Outline of experiment. (A) Illustration of the experimental setup. (B) Spectrum of the visible-pump pulse (green area), and visible-absorption band of IBr (black dashed curve). (C) Spectra of the XUV-probe pulse recorded with (dark blue area) and without (light blue area) the IBr sample, and the optical densitymore » (black dashed curve) calculated from the two spectra. The I-4d and Br-3d edges are covered by the broadband XUV spectrum. (D) Adiabatic potential energy curves of IBr, with the visible and XUV excitation pathways marked by vertical arrows. The red and blue wave packets represent the dissociation pathways from one-photon and two-photon processes, respectively. Avoided crossings are formed between the B and Y states (Rc = 3.3 Å) and Z and Y states (Rc = 2.8 Å). The inset shows the adiabatic and diabatic channels at the B/Y avoided crossing.« less
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    Works referencing / citing this record:

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    • The Journal of Chemical Physics, Vol. 151, Issue 21
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    Symmetry of molecular Rydberg states revealed by XUV transient absorption spectroscopy
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    Symmetry of Molecular Rydberg States Revealed by XUV Transient Absorption Spectroscopy
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    • Peng, Peng; Marceau, Claude; Hervé, Marius
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    • DOI: 10.1364/up.2020.th3b.4

    Symmetry of molecular Rydberg states revealed by XUV transient absorption spectroscopy
    journal, November 2019

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      Fig 1 (p. 17)figure
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      Fig S1 (p. 35)figure
      Fig S2 (p. 36)figure
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      Fig S5 (p. 39)figure
      Table S1 (p. 40)table
      Fig S6 (p. 41)figure
      Fig S7 (p. 42)figure
      Table S2 (p. 43)table
      Fig S8 (p. 44)figure
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