Search Menu
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information
Search Scholarly Publications

Title: Angle-dependent strong-field ionization of halomethanes

Abstract

We study, experimentally and theoretically, the ionization probability of singly halogenated methane molecules, CH3Cl and CH3Br, in intense linearly polarized 800 nm laser pulses as a function of the angle between the molecular axis and the laser polarization. Experimentally, the molecules are exposed to two laser pulses with a relative time delay. The first, weaker pulse induces a nuclear rotational wave packet within the molecules, which are then ionized by the second, stronger pulse. The angle-dependent ionization yields are extracted from fits of the measured delay-dependent ionization signal to a superposition of moments of the rotational wave packet’s angular distribution. Angle-dependent strong-field ionization (SFI) yields are also calculated using time-dependent density functional theory. Good agreement between measurements and theory is obtained. Interestingly, we find a marked difference between the angle-dependence of the ionization yields for these two halomethane species despite the similar structure of their highest occupied molecular orbitals. Calculations reveal that these differences are a result of multichannel (CH3Cl) vs single-channel (CH3Br) ionization and of increased hole localization on Br vs Cl. By adding calculations for CH3F, we can discern clear trends in the ionization dynamics with increasing halogen mass. These results are illustrative, as chemical functionalization and molecularmore » alignment are likely to be important parameters for initiating and controlling charge migration dynamics via SFI.« less

Authors:
ORCiD logo [1];  [2]; ORCiD logo [3];  [1];  [4]; ORCiD logo [4];  [3]; ORCiD logo [2];  [3];  [1]
+ Show Author Affiliations
  1. Univ. of Virginia, Charlottesville, VA (United States). Dept. of Physics
  2. Louisiana State Univ., Baton Rouge, LA (United States). Dept. of Chemistry
  3. Louisiana State Univ., Baton Rouge, LA (United States). Dept. of Physics and Astronomy
  4. The Ohio State Univ., Columbus, OH (United States). Dept. of Physics
Publication Date:
Research Org.:
Louisiana State Univ., Baton Rouge, LA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES)
OSTI Identifier:
1802356
Alternate Identifier(s):
OSTI ID: 1607571
Grant/Contract Number:  
SC0012462
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 151; Journal Issue: 19; 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

Citation Formats

Sándor, Péter, Sissay, Adonay, Mauger, François, Gordon, Mark W., Gorman, T. T., Scarborough, T. D., Gaarde, Mette B., Lopata, Kenneth, Schafer, K. J., and Jones, R. R. Angle-dependent strong-field ionization of halomethanes. United States: N. p., 2019. Web. doi:10.1063/1.5121711.
Copy to clipboard
Sándor, Péter, Sissay, Adonay, Mauger, François, Gordon, Mark W., Gorman, T. T., Scarborough, T. D., Gaarde, Mette B., Lopata, Kenneth, Schafer, K. J., & Jones, R. R. Angle-dependent strong-field ionization of halomethanes. United States. https://doi.org/10.1063/1.5121711
Copy to clipboard
Sándor, Péter, Sissay, Adonay, Mauger, François, Gordon, Mark W., Gorman, T. T., Scarborough, T. D., Gaarde, Mette B., Lopata, Kenneth, Schafer, K. J., and Jones, R. R. Thu . "Angle-dependent strong-field ionization of halomethanes". United States. https://doi.org/10.1063/1.5121711. https://www.osti.gov/servlets/purl/1802356.
Copy to clipboard
@article{osti_1802356,
title = {Angle-dependent strong-field ionization of halomethanes},
author = {Sándor, Péter and Sissay, Adonay and Mauger, François and Gordon, Mark W. and Gorman, T. T. and Scarborough, T. D. and Gaarde, Mette B. and Lopata, Kenneth and Schafer, K. J. and Jones, R. R.},
abstractNote = {We study, experimentally and theoretically, the ionization probability of singly halogenated methane molecules, CH3Cl and CH3Br, in intense linearly polarized 800 nm laser pulses as a function of the angle between the molecular axis and the laser polarization. Experimentally, the molecules are exposed to two laser pulses with a relative time delay. The first, weaker pulse induces a nuclear rotational wave packet within the molecules, which are then ionized by the second, stronger pulse. The angle-dependent ionization yields are extracted from fits of the measured delay-dependent ionization signal to a superposition of moments of the rotational wave packet’s angular distribution. Angle-dependent strong-field ionization (SFI) yields are also calculated using time-dependent density functional theory. Good agreement between measurements and theory is obtained. Interestingly, we find a marked difference between the angle-dependence of the ionization yields for these two halomethane species despite the similar structure of their highest occupied molecular orbitals. Calculations reveal that these differences are a result of multichannel (CH3Cl) vs single-channel (CH3Br) ionization and of increased hole localization on Br vs Cl. By adding calculations for CH3F, we can discern clear trends in the ionization dynamics with increasing halogen mass. These results are illustrative, as chemical functionalization and molecular alignment are likely to be important parameters for initiating and controlling charge migration dynamics via SFI.},
doi = {10.1063/1.5121711},
journal = {Journal of Chemical Physics},
number = 19,
volume = 151,
place = {United States},
year = {Thu Nov 21 00:00:00 EST 2019},
month = {Thu Nov 21 00:00:00 EST 2019}
}
Copy to clipboard
Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record
https://doi.org/10.1063/1.5121711
Copyright Statement
Other availability
Search WorldCat Search WorldCat to find libraries that may hold this journal
Citation Metrics:
Cited by: 23 works
Citation information provided by
Web of Science
Save / Share:
Export Metadata
Save to My Library
You must Sign In or Create an Account in order to save documents to your library.

Works referenced in this record:

Intense laser ionization of transiently aligned CO
journal, August 2005

Molecular polarizabilities and induced dipole moments in molecular mechanics
journal, January 2000

Direct Measurement of the Angular Dependence of Ionization for N 2 , O 2 , and CO 2 in Intense Laser Fields
journal, June 2007

Modeling Fast Electron Dynamics with Real-Time Time-Dependent Density Functional Theory: Application to Small Molecules and Chromophores
journal, April 2011

  • Lopata, Kenneth; Govind, Niranjan
  • Journal of Chemical Theory and Computation, Vol. 7, Issue 5
  • DOI: 10.1021/ct200137z

Using optimally tuned range separated hybrid functionals in ground-state calculations: Consequences and caveats
journal, May 2013

  • Karolewski, Andreas; Kronik, Leeor; Kümmel, Stephan
  • The Journal of Chemical Physics, Vol. 138, Issue 20
  • DOI: 10.1063/1.4807325

Multielectron Effects in the Strong Field Sequential Ionization of Aligned CH 3 I Molecules
journal, August 2017

  • Luo, Sizuo; Hu, Wenhui; Yu, Jiaqi
  • The Journal of Physical Chemistry A, Vol. 121, Issue 35
  • DOI: 10.1021/acs.jpca.7b05588

Attosecond science
journal, June 2007

  • Corkum, P. B.; Krausz, Ferenc
  • Nature Physics, Vol. 3, Issue 6
  • DOI: 10.1038/nphys620

Ab initio simulations of sodium using time-dependent density-functional theory
journal, November 1992

Strong field ionization rates simulated with time-dependent configuration interaction and an absorbing potential
journal, May 2014

  • Krause, Pascal; Sonk, Jason A.; Schlegel, H. Bernhard
  • The Journal of Chemical Physics, Vol. 140, Issue 17
  • DOI: 10.1063/1.4874156

Role of Multi-Electron Effects in the Asymmetry of Strong-Field Ionization and Fragmentation of Polar Molecules: The Methyl Halide Series
journal, November 2015

  • Walt, Samuel G.; Bhargava Ram, N.; von Conta, Aaron
  • The Journal of Physical Chemistry A, Vol. 119, Issue 49
  • DOI: 10.1021/acs.jpca.5b07331

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

Attosecond physics
journal, February 2009

octopus: a tool for the application of time-dependent density functional theory
journal, September 2006

  • Castro, Alberto; Appel, Heiko; Oliveira, Micael
  • physica status solidi (b), Vol. 243, Issue 11
  • DOI: 10.1002/pssb.200642067

Structure factors for tunneling ionization rates of molecules
journal, January 2013

Imaging ultrafast molecular dynamics with laser-induced electron diffraction
journal, March 2012

  • Blaga, Cosmin I.; Xu, Junliang; DiChiara, Anthony D.
  • Nature, Vol. 483, Issue 7388
  • DOI: 10.1038/nature10820

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

Time-dependent local-density approximation in real time
journal, August 1996

NWChem: A comprehensive and scalable open-source solution for large scale molecular simulations
journal, September 2010

  • Valiev, M.; Bylaska, E. J.; Govind, N.
  • Computer Physics Communications, Vol. 181, Issue 9, p. 1477-1489
  • DOI: 10.1016/j.cpc.2010.04.018

Angular Dependence of Strong Field Ionization of CH 3 X (X = F, Cl, Br, or I) Using Time-Dependent Configuration Interaction with an Absorbing Potential
journal, July 2017

  • Hoerner, Paul; Schlegel, H. Bernhard
  • The Journal of Physical Chemistry A, Vol. 121, Issue 31
  • DOI: 10.1021/acs.jpca.7b06108

Angle-Dependent Ionization of Small Molecules by Time-Dependent Configuration Interaction and an Absorbing Potential
journal, May 2015

Terahertz-Induced Field-Free Orientation of Rotationally Excited Molecules
journal, March 2014

Time-dependent density-functional study of the alignment-dependent ionization of acetylene and ethylene by strong laser pulses
journal, February 2015

Alignment-dependent strong-field ionization yields of carbonyl sulfide molecules induced by mid-infrared laser pulses
journal, September 2016

  • Johansen, Rasmus; Bay, Kathrine Glerup; Christensen, Lauge
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 49, Issue 20
  • DOI: 10.1088/0953-4075/49/20/205601

Angle-dependent strong-field molecular ionization rates with tuned range-separated time-dependent density functional theory
journal, September 2016

  • Sissay, Adonay; Abanador, Paul; Mauger, François
  • The Journal of Chemical Physics, Vol. 145, Issue 9
  • DOI: 10.1063/1.4961731

Molecular Frame Reconstruction Using Time-Domain Photoionization Interferometry
journal, August 2017

Diffraction using laser-driven broadband electron wave packets
journal, August 2014

  • Xu, Junliang; Blaga, Cosmin I.; Zhang, Kaikai
  • Nature Communications, Vol. 5, Issue 1
  • DOI: 10.1038/ncomms5635

Intense-field laser ionization rates in atoms and molecules
journal, June 2001

Electron dynamics with real-time time-dependent density functional theory
journal, February 2016

  • Provorse, Makenzie R.; Isborn, Christine M.
  • International Journal of Quantum Chemistry, Vol. 116, Issue 10
  • DOI: 10.1002/qua.25096

Cooling of large molecules below 1 K and He clusters formation
journal, May 2000

  • Even, U.; Jortner, J.; Noy, D.
  • The Journal of Chemical Physics, Vol. 112, Issue 18
  • DOI: 10.1063/1.481405

Density Functional Theory with Correct Long-Range Asymptotic Behavior
journal, February 2005

The Ground-State Rotational Constants of Methyl Bromide
journal, August 1986

Orientation-dependent ionization yields from strong-field ionization of fixed-in-space linear and asymmetric top molecules
journal, December 2011

  • Hansen, Jonas L.; Holmegaard, Lotte; Nielsen, Jens H.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 45, Issue 1
  • DOI: 10.1088/0953-4075/45/1/015101

Attosecond physics
conference, January 2007

  • Kienberger, Reinhard; Krausz, Ferenc
  • ICALEO® 2007: 26th International Congress on Laser Materials Processing, Laser Microprocessing and Nanomanufacturing, International Congress on Applications of Lasers & Electro-Optics
  • DOI: 10.2351/1.5061046

Disentangling Strong-Field Multielectron Dynamics with Angular Streaking
journal, April 2018

  • Winney, Alexander H.; Basnayake, Gihan; Debrah, Duke A.
  • The Journal of Physical Chemistry Letters, Vol. 9, Issue 10
  • DOI: 10.1021/acs.jpclett.8b00028

Alignment-Dependent Strong Field Ionization of Molecules
journal, June 2003

Laser-Induced Electron Tunneling and Diffraction
journal, June 2008

Phase-sensitive molecular ionization induced by a phase-controlled two-color laser field in methyl halides
journal, October 2006

A time-dependent Hartree–Fock approach for studying the electronic optical response of molecules in intense fields
journal, January 2005

  • Li, Xiaosong; Smith, Stanley M.; Markevitch, Alexei N.
  • Phys. Chem. Chem. Phys., Vol. 7, Issue 2
  • DOI: 10.1039/b415849k

Tuned Range-Separated Hybrids in Density Functional Theory
journal, March 2010

Angular Dependence of Strong Field Ionization of Haloacetylenes HCCX (X = F, Cl, Br, I), Using Time-Dependent Configuration Interaction with an Absorbing Potential
journal, December 2017

  • Hoerner, Paul; Schlegel, H. Bernhard
  • The Journal of Physical Chemistry C, Vol. 122, Issue 25
  • DOI: 10.1021/acs.jpcc.8b00619

Measuring ultrashort laser pulses in the time-frequency domain using frequency-resolved optical gating
journal, September 1997

  • Trebino, Rick; DeLong, Kenneth W.; Fittinghoff, David N.
  • Review of Scientific Instruments, Vol. 68, Issue 9, p. 3277-3295
  • DOI: 10.1063/1.1148286

Theory of molecular tunneling ionization
journal, September 2002

Plasma perspective on strong field multiphoton ionization
journal, September 1993

Efficient first-principles electronic dynamics
journal, May 2011

  • Liang, Wenkel; Chapman, Craig T.; Li, Xiaosong
  • The Journal of Chemical Physics, Vol. 134, Issue 18
  • DOI: 10.1063/1.3589144
    Sort by:
    [ × clear filter / sort ]

    Similar Records in DOE PAGES and OSTI.GOV collections: