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Title: Precise Access to the Molecular-Frame Complex Recombination Dipole through High-Harmonic Spectroscopy

Authors:
; ; ; ; ;
Publication Date:
Sponsoring Org.:
USDOE
OSTI Identifier:
1341314
Grant/Contract Number:
FG02-04ER15614; FG02-06ER15833
Resource Type:
Journal Article: Publisher's Accepted Manuscript
Journal Name:
Physical Review Letters
Additional Journal Information:
Journal Volume: 118; Journal Issue: 3; Related Information: CHORUS Timestamp: 2017-01-24 16:41:23; Journal ID: ISSN 0031-9007
Publisher:
American Physical Society
Country of Publication:
United States
Language:
English

Citation Formats

Schoun, S. B., Camper, A., Salières, P., Lucchese, R. R., Agostini, P., and DiMauro, L. F. Precise Access to the Molecular-Frame Complex Recombination Dipole through High-Harmonic Spectroscopy. United States: N. p., 2017. Web. doi:10.1103/PhysRevLett.118.033201.
Schoun, S. B., Camper, A., Salières, P., Lucchese, R. R., Agostini, P., & DiMauro, L. F. Precise Access to the Molecular-Frame Complex Recombination Dipole through High-Harmonic Spectroscopy. United States. doi:10.1103/PhysRevLett.118.033201.
Schoun, S. B., Camper, A., Salières, P., Lucchese, R. R., Agostini, P., and DiMauro, L. F. Thu . "Precise Access to the Molecular-Frame Complex Recombination Dipole through High-Harmonic Spectroscopy". United States. doi:10.1103/PhysRevLett.118.033201.
@article{osti_1341314,
title = {Precise Access to the Molecular-Frame Complex Recombination Dipole through High-Harmonic Spectroscopy},
author = {Schoun, S. B. and Camper, A. and Salières, P. and Lucchese, R. R. and Agostini, P. and DiMauro, L. F.},
abstractNote = {},
doi = {10.1103/PhysRevLett.118.033201},
journal = {Physical Review Letters},
number = 3,
volume = 118,
place = {United States},
year = {Thu Jan 19 00:00:00 EST 2017},
month = {Thu Jan 19 00:00:00 EST 2017}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record at 10.1103/PhysRevLett.118.033201

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  • High-order harmonic generation (HHG) from molecules produces spectra that are modulated by interferences that encode both the static structure and the electron dynamics initiated by interaction with the laser field. Using a midinfrared (mid-IR) laser at 1300 nm, we are able to study the region of the harmonic spectrum containing such interferences in CO{sub 2} over a wide range of intensities. This allows for isolation and characterization of interference minima arising due to subcycle electronic dynamics triggered by the laser field, which had previously been identified but not systematically separated. Our experimental and theoretical results demonstrate important steps toward combiningmore » attosecond temporal and angstrom-scale spatial resolution in molecular HHG imaging.« less
  • We demonstrate that high-order-harmonic generation (HHG) spectroscopy can be used to probe stereoisomers of randomly oriented 1,2-dichloroethylene (C{sub 2}H{sub 2}Cl{sub 2}) and 2-butene (C{sub 4}H{sub 8}). The high-harmonic spectra of these isomers are distinguishable over a range of laser intensities and wavelengths. Time-dependent numerical calculations of angle-dependent ionization yields for 1,2-dichloroethylene suggest that the harmonic spectra of molecular isomers reflect differences in their strong-field ionization. The subcycle ionization yields for the cis isomer are an order of magnitude higher than those for the trans isomer. The sensitivity in discrimination of the harmonic spectra of cis- and trans- isomers is greatermore » than 8 and 5 for 1,2-dichloroethylene and 2-butene, respectively. We show that HHG spectroscopy cannot differentiate the harmonic spectra of the two enantiomers of the chiral molecule propylene oxide (C{sub 3}H{sub 6}O).« less
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  • We quantitatively interpret the recently discovered intriguing phenomenon related to resonance Hyper-Raman (HR) scattering. In resonance HR spectra of all-trans-β-carotene (β-carotene) in solution, vibrations of proximate solvent molecules are observed concomitantly with the solute β-carotene HR bands. It has been shown that these solvent bands are subject to marked intensity enhancements by more than 5 orders of magnitude under the presence of β-carotene. We have called this phenomenon the molecular-near field effect. Resonance HR spectra of β-carotene in benzene, deuterated benzene, cyclohexane, and deuterated cyclohexane have been measured precisely for a quantitative analysis of this effect. The assignments of themore » observed peaks are made by referring to the infrared, Raman, and HR spectra of neat solvents. It has been revealed that infrared active and some Raman active vibrations are active in the HR molecular near-field effect. The observed spectra in the form of difference spectra (between benzene/deuterated benzene and cyclohexane/deuterated cyclohexane) are quantitatively analyzed on the basis of the extended vibronic theory of resonance HR scattering. The theory incorporates the coupling of excited electronic states of β-carotene with the vibrations of a proximate solvent molecule through solute–solvent dipole–dipole and dipole–quadrupole interactions. It is shown that the infrared active modes arise from the dipole–dipole interaction, whereas Raman active modes from the dipole–quadrupole interaction. It is also shown that vibrations that give strongly polarized Raman bands are weak in the HR molecular near-field effect. The observed solvent HR spectra are simulated with the help of quantum chemical calculations for various orientations and distances of a solvent molecule with respect to the solute. The observed spectra are best simulated with random orientations of the solvent molecule at an intermolecular distance of 10 Å.« less
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