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Title: Optimized pulses for Raman excitation through the continuum: Verification using the multiconfigurational time-dependent Hartree-Fock method

Abstract

Here, we have verified a mechanism for Raman excitation of atoms through continuum levels previously obtained by quantum optimal control using the multiconfigurational time-dependent Hartree-Fock (MCTDHF) method. For the optimal control, which requires running multiple propagations to determine the optimal pulse sequence, we used the computationally inexpensive time-dependent configuration interaction singles (TDCIS) method. TDCIS captures all of the necessary correlation of the desired processes but assumes that ionization pathways reached via double excitations are not present. MCTDHF includes these pathways and all multiparticle correlations in a set of time-dependent orbitals. The mechanism that was determined to be optimal in the Raman excitation of the Ne 1s 22s 22p 53p 1 valence state via the metastable 1s 22s 12p 63p 1 resonance state involves a sequential resonance-valence excitation. First, a long pump pulse excites the core-hole state, and then a shorter Stokes pulse transfers the population to the valence state. This process represents the first step in a multidimensional x-ray spectroscopy scheme that will provide a local probe of valence electronic correlations. Although at the optimal pulse intensities at the TDCIS level of theory the MCTDHF method predicts multiple ionization or excitation ionization of the atom, at slightly lower intensities (reducedmore » by a factor of about 4) the TDCIS mechanism is shown to hold qualitatively. Quantitatively, the MCTDHF populations are reduced from the TDCIS calculations by a factor of 4.« less

Authors:
 [1];  [1];  [2];  [3]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States). Kenneth S. Pitzer Center for Theoretical Chemistry and Dept. of Chemistry
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Davis, CA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Advanced Scientific Computing Research (ASCR) (SC-21; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
OSTI Identifier:
1465413
Alternate Identifier(s):
OSTI ID: 1369580
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Journal Article: Accepted Manuscript
Journal Name:
Physical Review A
Additional Journal Information:
Journal Volume: 96; Journal Issue: 1; Related Information: © 2017 American Physical Society.; Journal ID: ISSN 2469-9926
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY; 47 OTHER INSTRUMENTATION; coherent control; electron correlation calculations; multiphonon or tunneling ionization and excitation

Citation Formats

Greenman, Loren, Whaley, K. Birgitta, Haxton, Daniel J., and McCurdy, C. William. Optimized pulses for Raman excitation through the continuum: Verification using the multiconfigurational time-dependent Hartree-Fock method. United States: N. p., 2017. Web. doi:10.1103/PhysRevA.96.013411.
Greenman, Loren, Whaley, K. Birgitta, Haxton, Daniel J., & McCurdy, C. William. Optimized pulses for Raman excitation through the continuum: Verification using the multiconfigurational time-dependent Hartree-Fock method. United States. doi:10.1103/PhysRevA.96.013411.
Greenman, Loren, Whaley, K. Birgitta, Haxton, Daniel J., and McCurdy, C. William. Thu . "Optimized pulses for Raman excitation through the continuum: Verification using the multiconfigurational time-dependent Hartree-Fock method". United States. doi:10.1103/PhysRevA.96.013411. https://www.osti.gov/servlets/purl/1465413.
@article{osti_1465413,
title = {Optimized pulses for Raman excitation through the continuum: Verification using the multiconfigurational time-dependent Hartree-Fock method},
author = {Greenman, Loren and Whaley, K. Birgitta and Haxton, Daniel J. and McCurdy, C. William},
abstractNote = {Here, we have verified a mechanism for Raman excitation of atoms through continuum levels previously obtained by quantum optimal control using the multiconfigurational time-dependent Hartree-Fock (MCTDHF) method. For the optimal control, which requires running multiple propagations to determine the optimal pulse sequence, we used the computationally inexpensive time-dependent configuration interaction singles (TDCIS) method. TDCIS captures all of the necessary correlation of the desired processes but assumes that ionization pathways reached via double excitations are not present. MCTDHF includes these pathways and all multiparticle correlations in a set of time-dependent orbitals. The mechanism that was determined to be optimal in the Raman excitation of the Ne 1s22s22p53p1 valence state via the metastable 1s22s12p63p1 resonance state involves a sequential resonance-valence excitation. First, a long pump pulse excites the core-hole state, and then a shorter Stokes pulse transfers the population to the valence state. This process represents the first step in a multidimensional x-ray spectroscopy scheme that will provide a local probe of valence electronic correlations. Although at the optimal pulse intensities at the TDCIS level of theory the MCTDHF method predicts multiple ionization or excitation ionization of the atom, at slightly lower intensities (reduced by a factor of about 4) the TDCIS mechanism is shown to hold qualitatively. Quantitatively, the MCTDHF populations are reduced from the TDCIS calculations by a factor of 4.},
doi = {10.1103/PhysRevA.96.013411},
journal = {Physical Review A},
number = 1,
volume = 96,
place = {United States},
year = {Thu Jul 13 00:00:00 EDT 2017},
month = {Thu Jul 13 00:00:00 EDT 2017}
}

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Works referenced in this record:

Two-dimensional stimulated resonance Raman spectroscopy of molecules with broadband x-ray pulses
journal, May 2012

  • Biggs, Jason D.; Zhang, Yu; Healion, Daniel
  • The Journal of Chemical Physics, Vol. 136, Issue 17, Article No. 174117
  • DOI: 10.1063/1.4706899