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Title: Ultrafast X-ray Absorption Near Edge Structure Reveals Ballistic Excited State Structural Dynamics

Abstract

Here, polarized ultrafast time-resolved X-ray absorption near edge structure (XANES) allows characterization of excited state dynamics following excitation. Excitation of vitamin B 12, cyanocobalamin (CNCbl), in the αβ-band at 550 nm and the γ-band at 365 nm was used to uniquely resolve axial and equatorial contributions to the excited state dynamics. The structural evolution of the excited molecule is best described by a coherent ballistic trajectory on the excited state potential energy surface. Prompt expansion of the Co cavity by ca. 0.03 Å is followed by significant elongation of the axial bonds (>0.25 Å) over the first 190 fs. Subsequent contraction of the Co cavity in both axial and equatorial directions results in the relaxed S 1 excited state structure within 500 fs of excitation.

Authors:
 [1]; ORCiD logo [1];  [2];  [2];  [1]; ORCiD logo [1];  [1];  [3];  [1];  [2];  [4];  [1];  [2];  [5]; ORCiD logo [1];  [1]; ORCiD logo [1]
  1. Univ. of Michigan, Ann Arbor, MI (United States)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. SLAC National Accelerator Lab., Menlo Park, CA (United States); European XFEL GmbH, Schenefeld (Germany)
  4. Univ. of Louisville, Louisville, KY (United States)
  5. Univ. of Louisville, Louisville, KY (United States); Univ. of Gdansk, Gdansk (Poland)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22)
OSTI Identifier:
1470935
Grant/Contract Number:  
[CHE 1428479; CHE 1565795; CHE-1464584; AC02-76SF00515; UMO-2015/17/B/ST4/ 03733]
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
Additional Journal Information:
[ Journal Volume: 122; Journal Issue: 22]; Journal ID: ISSN 1089-5639
Publisher:
American Chemical Society
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Miller, Nicholas A., Deb, Aniruddha, Alonso-Mori, Roberto, Glownia, James M., Kiefer, Laura M., Konar, Arkaprabha, Michocki, Lindsay B., Sikorski, Marcin, Sofferman, Danielle L., Song, Sanghoon, Toda, Megan J., Wiley, Theodore E., Zhu, Diling, Kozlowski, Pawel M., Kubarych, Kevin J., Penner-Hahn, James E., and Sension, Roseanne J. Ultrafast X-ray Absorption Near Edge Structure Reveals Ballistic Excited State Structural Dynamics. United States: N. p., 2018. Web. doi:10.1021/acs.jpca.8b04223.
Miller, Nicholas A., Deb, Aniruddha, Alonso-Mori, Roberto, Glownia, James M., Kiefer, Laura M., Konar, Arkaprabha, Michocki, Lindsay B., Sikorski, Marcin, Sofferman, Danielle L., Song, Sanghoon, Toda, Megan J., Wiley, Theodore E., Zhu, Diling, Kozlowski, Pawel M., Kubarych, Kevin J., Penner-Hahn, James E., & Sension, Roseanne J. Ultrafast X-ray Absorption Near Edge Structure Reveals Ballistic Excited State Structural Dynamics. United States. doi:10.1021/acs.jpca.8b04223.
Miller, Nicholas A., Deb, Aniruddha, Alonso-Mori, Roberto, Glownia, James M., Kiefer, Laura M., Konar, Arkaprabha, Michocki, Lindsay B., Sikorski, Marcin, Sofferman, Danielle L., Song, Sanghoon, Toda, Megan J., Wiley, Theodore E., Zhu, Diling, Kozlowski, Pawel M., Kubarych, Kevin J., Penner-Hahn, James E., and Sension, Roseanne J. Fri . "Ultrafast X-ray Absorption Near Edge Structure Reveals Ballistic Excited State Structural Dynamics". United States. doi:10.1021/acs.jpca.8b04223. https://www.osti.gov/servlets/purl/1470935.
@article{osti_1470935,
title = {Ultrafast X-ray Absorption Near Edge Structure Reveals Ballistic Excited State Structural Dynamics},
author = {Miller, Nicholas A. and Deb, Aniruddha and Alonso-Mori, Roberto and Glownia, James M. and Kiefer, Laura M. and Konar, Arkaprabha and Michocki, Lindsay B. and Sikorski, Marcin and Sofferman, Danielle L. and Song, Sanghoon and Toda, Megan J. and Wiley, Theodore E. and Zhu, Diling and Kozlowski, Pawel M. and Kubarych, Kevin J. and Penner-Hahn, James E. and Sension, Roseanne J.},
abstractNote = {Here, polarized ultrafast time-resolved X-ray absorption near edge structure (XANES) allows characterization of excited state dynamics following excitation. Excitation of vitamin B12, cyanocobalamin (CNCbl), in the αβ-band at 550 nm and the γ-band at 365 nm was used to uniquely resolve axial and equatorial contributions to the excited state dynamics. The structural evolution of the excited molecule is best described by a coherent ballistic trajectory on the excited state potential energy surface. Prompt expansion of the Co cavity by ca. 0.03 Å is followed by significant elongation of the axial bonds (>0.25 Å) over the first 190 fs. Subsequent contraction of the Co cavity in both axial and equatorial directions results in the relaxed S1 excited state structure within 500 fs of excitation.},
doi = {10.1021/acs.jpca.8b04223},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = [22],
volume = [122],
place = {United States},
year = {2018},
month = {5}
}

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