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Title: Probing the interplay between geometric and electronic-structure features via high-harmonic spectroscopy

Abstract

We present molecular-frame measurements of the recombination dipole matrix element (RDME) in CO2, N2O, and carbonyl sulfide (OCS) molecules using high-harmonic spectroscopy. Both the amplitudes and phases of the RDMEs exhibit clear imprints of a two-center interference minimum, which moves in energy with the molecular alignment angle relative to the laser polarization. Here, we find that whereas the angle dependence of this minimum is consistent with the molecular geometry in CO2 and N2O, it behaves very differently in OCS; in particular, the phase shift which accompanies the two-center minimum changes sign for different alignment angles. Our results suggest that two interfering structural features contribute to the OCS RDME, namely, (i) the geometrical two-center minimum and (ii) a Cooper-like, electronic-structure minimum associated with the sulfur end of the molecule. We compare our results to ab initio calculations using time-dependent density functional theory and present an empirical model that captures both the two-center and the Cooper-like interferences. We also show that the yield from unaligned samples of two-center molecules is, in general, reduced at high photon energies compared to aligned samples, due to the destructive interference between molecules with different alignments.

Authors:
 [1]; ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [2];  [1]; ORCiD logo [3];  [3]; ORCiD logo [2];  [2];  [1];  [2];  [1]
  1. The Ohio State Univ., Columbus, OH (United States)
  2. Louisiana State Univ., Baton Rouge, LA (United States)
  3. Univ. of Virginia, Charlottesville, VA (United States)
Publication Date:
Research Org.:
The Ohio State Univ., Columbus, OH (United States); Louisiana State Univ., Baton Rouge, LA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1609522
Alternate Identifier(s):
OSTI ID: 1512532
Grant/Contract Number:  
FG02-04ER15614; SC0012462
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 150; Journal Issue: 18; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; chemistry; physics

Citation Formats

Gorman, T. T., Scarborough, T. D., Abanador, P. M., Mauger, F., Kiesewetter, D., Sándor, P., Khatri, S., Lopata, K., Schafer, K. J., Agostini, P., Gaarde, M. B., and DiMauro, L. F. Probing the interplay between geometric and electronic-structure features via high-harmonic spectroscopy. United States: N. p., 2019. Web. doi:10.1063/1.5086036.
Gorman, T. T., Scarborough, T. D., Abanador, P. M., Mauger, F., Kiesewetter, D., Sándor, P., Khatri, S., Lopata, K., Schafer, K. J., Agostini, P., Gaarde, M. B., & DiMauro, L. F. Probing the interplay between geometric and electronic-structure features via high-harmonic spectroscopy. United States. https://doi.org/10.1063/1.5086036
Gorman, T. T., Scarborough, T. D., Abanador, P. M., Mauger, F., Kiesewetter, D., Sándor, P., Khatri, S., Lopata, K., Schafer, K. J., Agostini, P., Gaarde, M. B., and DiMauro, L. F. Tue . "Probing the interplay between geometric and electronic-structure features via high-harmonic spectroscopy". United States. https://doi.org/10.1063/1.5086036. https://www.osti.gov/servlets/purl/1609522.
@article{osti_1609522,
title = {Probing the interplay between geometric and electronic-structure features via high-harmonic spectroscopy},
author = {Gorman, T. T. and Scarborough, T. D. and Abanador, P. M. and Mauger, F. and Kiesewetter, D. and Sándor, P. and Khatri, S. and Lopata, K. and Schafer, K. J. and Agostini, P. and Gaarde, M. B. and DiMauro, L. F.},
abstractNote = {We present molecular-frame measurements of the recombination dipole matrix element (RDME) in CO2, N2O, and carbonyl sulfide (OCS) molecules using high-harmonic spectroscopy. Both the amplitudes and phases of the RDMEs exhibit clear imprints of a two-center interference minimum, which moves in energy with the molecular alignment angle relative to the laser polarization. Here, we find that whereas the angle dependence of this minimum is consistent with the molecular geometry in CO2 and N2O, it behaves very differently in OCS; in particular, the phase shift which accompanies the two-center minimum changes sign for different alignment angles. Our results suggest that two interfering structural features contribute to the OCS RDME, namely, (i) the geometrical two-center minimum and (ii) a Cooper-like, electronic-structure minimum associated with the sulfur end of the molecule. We compare our results to ab initio calculations using time-dependent density functional theory and present an empirical model that captures both the two-center and the Cooper-like interferences. We also show that the yield from unaligned samples of two-center molecules is, in general, reduced at high photon energies compared to aligned samples, due to the destructive interference between molecules with different alignments.},
doi = {10.1063/1.5086036},
journal = {Journal of Chemical Physics},
number = 18,
volume = 150,
place = {United States},
year = {Tue May 14 00:00:00 EDT 2019},
month = {Tue May 14 00:00:00 EDT 2019}
}

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Works referencing / citing this record:

High-harmonic spectroscopy of transient two-center interference calculated with time-dependent density-functional theory
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Shaping attosecond pulses by controlling the minima in high-order harmonic generation through alignment of CO 2 molecules
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Influence of dynamic core-electron polarization on the structural minimum in high-order harmonics of CO 2 molecules
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