skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

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. 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., and DiMauro, L. F. Tue . "Probing the interplay between geometric and electronic-structure features via high-harmonic spectroscopy". United States. doi: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 = {2019},
month = {5}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 2 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Precise Access to the Molecular-Frame Complex Recombination Dipole through High-Harmonic Spectroscopy
journal, January 2017


Photoelectron dynamics of the cooper minimum in free molecules
journal, December 1986

  • Carlson, T. A.; Krause, M. O.; Svensson, W. A.
  • Zeitschrift f�r Physik D Atoms, Molecules and Clusters, Vol. 2, Issue 4
  • DOI: 10.1007/bf01426235

Generalized molecular orbital tomography
journal, June 2011

  • Vozzi, C.; Negro, M.; Calegari, F.
  • Nature Physics, Vol. 7, Issue 10
  • DOI: 10.1038/nphys2029

Angle dependence of strong-field single and double ionization of carbonyl sulfide
journal, October 2018


Field-induced orbital distortion in high-order-harmonic generation from aligned and oriented molecules within adiabatic strong-field approximation
journal, April 2014


Absolute oscillator strengths for valence-shell ionic photofragmentations of N2O and CO2 (8–75 eV)
journal, February 1980


Molecular Recollision Interferometry in High Harmonic Generation
journal, February 2008


High Harmonic Spectroscopy of the Cooper Minimum in Molecules
journal, January 2013


Photoionization from Outer Atomic Subshells. A Model Study
journal, October 1962


Multielectron corrections in molecular high-order harmonic generation for different formulations of the strong-field approximation
journal, July 2011


Semiclassical-wave-function perspective on high-harmonic generation
journal, April 2016


Accessing properties of electron wave packets generated by attosecond pulse trains through time-dependent calculations
journal, July 2005


High-order harmonic generation in rare gases with a 1-ps 1053-nm laser
journal, February 1993


Above threshold ionization beyond the high harmonic cutoff
journal, March 1993


Measurement and laser control of attosecond charge migration in ionized iodoacetylene
journal, October 2015


Phase of the atomic polarization in high-order harmonic generation
journal, December 1995

  • Lewenstein, Maciej; Salières, Pascal; L’Huillier, Anne
  • Physical Review A, Vol. 52, Issue 6
  • DOI: 10.1103/physreva.52.4747

Erratum: Two-center minima in harmonic spectra from aligned polar molecules [Phys. Rev. A 84 , 023418 (2011)]
journal, November 2011


Angle resolved photoelectron spectroscopy of CS 2 and COS measured as a function of photon energy from 21 to 70 eV
journal, August 1982

  • Carlson, Thomas A.; Krause, Manfred O.; Grimm, Frederick A.
  • The Journal of Chemical Physics, Vol. 77, Issue 4
  • DOI: 10.1063/1.444067

Fluorescence-lifetime measurements in atmospheric-pressure flames using nanosecond-pulsed lasers
journal, February 2002


Controlling the Interference of Multiple Molecular Orbitals in High-Harmonic Generation
journal, June 2010


Partial oscillator strengths for the photoionization of N2O and CO2 (20–60 eV)
journal, November 1978


Real-space grids and the Octopus code as tools for the development of new simulation approaches for electronic systems
journal, January 2015

  • Andrade, Xavier; Strubbe, David; De Giovannini, Umberto
  • Physical Chemistry Chemical Physics, Vol. 17, Issue 47
  • DOI: 10.1039/c5cp00351b

Tomographic imaging of molecular orbitals
journal, December 2004


Strong-field rescattering physics—self-imaging of a molecule by its own electrons
journal, June 2010

  • Lin, C. D.; Le, Anh-Thu; Chen, Zhangjin
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 43, Issue 12
  • DOI: 10.1088/0953-4075/43/12/122001

Signatures of symmetry and electronic structure in high-order harmonic generation in polyatomic molecules
journal, June 2010


Observation of Electronic Structure Minima in High-Harmonic Generation
journal, March 2009


Analytic formulae for high harmonic generation
journal, January 2009

  • Frolov, M. V.; Manakov, N. L.; Sarantseva, T. S.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 42, Issue 3
  • DOI: 10.1088/0953-4075/42/3/035601

Multi-channel dynamics in high harmonic generation of aligned CO 2 : ab initio analysis with time-dependent B-spline algebraic diagrammatic construction
journal, January 2018

  • Ruberti, M.; Decleva, P.; Averbukh, V.
  • Physical Chemistry Chemical Physics, Vol. 20, Issue 12
  • DOI: 10.1039/c7cp07849h

Coherent control of attosecond emission from aligned molecules
journal, May 2008

  • Boutu, W.; Haessler, S.; Merdji, H.
  • Nature Physics, Vol. 4, Issue 7
  • DOI: 10.1038/nphys964

Attosecond Charge Migration with TDDFT: Accurate Dynamics from a Well-Defined Initial State
journal, August 2017

  • Bruner, Adam; Hernandez, Samuel; Mauger, François
  • The Journal of Physical Chemistry Letters, Vol. 8, Issue 17
  • DOI: 10.1021/acs.jpclett.7b01652

Absolute dipole oscillator strengths for the photo-ionization and photoabsorption of COS (5–50 eV)
journal, January 1981

  • White, M. G.; Leung, K. T.; Brion, C. E.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 23, Issue 2
  • DOI: 10.1016/0368-2048(81)80030-8

Quantum interference and multielectron effects in high-harmonic spectra of polar molecules
journal, March 2013


Temporal Coherence of Ultrashort High-Order Harmonic Pulses
journal, July 1998


Electronic Structures of Molecules XIV. Linear Triatomic Molecules, Especially Carbon Dioxide
journal, November 1935

  • Mulliken, Robert S.
  • The Journal of Chemical Physics, Vol. 3, Issue 11
  • DOI: 10.1063/1.1749583

Multiple-harmonic generation in rare gases at high laser intensity
journal, June 1989


Attosecond imaging of molecular electronic wavepackets
journal, January 2010

  • Haessler, S.; Caillat, J.; Boutu, W.
  • Nature Physics, Vol. 6, Issue 3
  • DOI: 10.1038/nphys1511

Full Characterization of a Molecular Cooper Minimum Using High-Harmonic Spectroscopy
journal, July 2018

  • Scarborough, Timothy; Gorman, Timothy; Mauger, François
  • Applied Sciences, Vol. 8, Issue 7
  • DOI: 10.3390/app8071129

High-Harmonic Spectroscopy of Oriented OCS Molecules: Emission of Even and Odd Harmonics
journal, December 2012


Time-dependent density-functional-theory calculation of high-order-harmonic generation of H 2
journal, May 2012


Attosecond Pulse Shaping around a Cooper Minimum
journal, April 2014


Attosecond Pulse Trains Using High–Order Harmonics
journal, August 1996


Attosecond Synchronization of High-Harmonic Soft X-rays
journal, November 2003


Direct extraction of intense-field-induced polarization in the continuum on the attosecond time scale from transient absorption
journal, February 2016


High harmonic interferometry of multi-electron dynamics in molecules
journal, July 2009

  • Smirnova, Olga; Mairesse, Yann; Patchkovskii, Serguei
  • Nature, Vol. 460, Issue 7258
  • DOI: 10.1038/nature08253

Comparison of self-interaction-corrections for metal clusters
journal, February 2002

  • Legrand, C.; Suraud, E.; Reinhard, P-G
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 35, Issue 4
  • DOI: 10.1088/0953-4075/35/4/333

Plasma perspective on strong field multiphoton ionization
journal, September 1993


Quantitative rescattering theory of high-order harmonic generation for polyatomic molecules
journal, June 2013


    Works referencing / citing this record:

    High-harmonic spectroscopy of transient two-center interference calculated with time-dependent density-functional theory
    journal, July 2019

    • Mauger, François; Abanador, Paul M.; Scarborough, Timothy D.
    • Structural Dynamics, Vol. 6, Issue 4
    • DOI: 10.1063/1.5111349

    Influence of dynamic core-electron polarization on the structural minimum in high-order harmonics of CO 2 molecules
    journal, November 2019


    Shaping attosecond pulses by controlling the minima in high-order harmonic generation through alignment of CO 2 molecules
    journal, January 2020