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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-4 dand Br-3 dcore-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]
  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 Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22); 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.
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. doi:10.1126/science.aax0076.
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. doi:10.1126/science.aax0076.
@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 = {2019},
month = {7}
}

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