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Ultrafast Rydberg-state dissociation in oxygen: Identifying the role of multielectron excitations

Journal Article · · Physical Review A
 [1];  [1];  [2];  [3];  [1]
  1. Univ. of Arizona, Tucson, AZ (United States)
  2. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
  3. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Davis, CA (United States)
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We investigated the fragmentation dynamics of highly excited states of molecular oxygen using femtosecond transient photoelectron spectroscopy. An extreme ultraviolet (XUV) pulse populates the autoionizing Rydberg series converging to O$$_2^+$$c4Σ$$_u^-$$, and a femtosecond near-infrared (IR) pulse was used to photoionize these states as they dissociate. Monitoring the differential photoelectron spectra as a function of time delay allowed us to obtain the relaxation lifetimes of these Rydberg states. We observed a photoelectron signal corresponding to the formation of a 4p excited atomic oxygen fragment, which is not an expected dissociation product of the (O$$_2^+$$c4Σ$$_u^-$$)nlσg Rydberg series. Analysis of the time-dependent photoelectron spectra and photoionization calculations indicate that this fragment results from a previously unexplored (O$$_2^+$$ 4II$$_g$$)4p repulsive state and that, contrary to expectations, this multielectron excitation pathway presents a substantial cross section. Here, our study demonstrates that two-color time-resolved differential photoelectron spectroscopy is an excellent tool to study the fragmentation dynamics of such multielectron excited states, which are not easily probed by other means.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division
Grant/Contract Number:
AC02-05CH11231; SC0018251
OSTI ID:
1542413
Alternate ID(s):
OSTI ID: 1546301
Journal Information:
Physical Review A, Journal Name: Physical Review A Journal Issue: 6 Vol. 99; ISSN PLRAAN; ISSN 2469-9926
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

References (47)

Molpro: a general-purpose quantum chemistry program package: Molpro
  • Werner, Hans-Joachim; Knowles, Peter J.; Knizia, Gerald
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 2, Issue 2 https://doi.org/10.1002/wcms.82
journal July 2011
Extreme ultraviolet photodissociation of O2 via the free (c 4Σ−u)3sσg state as probed by dispersed vacuum ultraviolet fluorescence journal July 1992
Assignments of autoionization states of O2 journal January 1987
A study of the absolute photoabsorption, photoionization and photodissociation cross sections and the photoionization quantum efficiency of oxygen from the ionization threshold to 490 Å journal June 1993
High-resolution threshold photoelectron spectrum of molecular oxygen journal July 1993
Dissociative photoionization study of O2 journal June 1998
Interaction of vacuum ultraviolet photons with molecules. Formation and dissociation dynamics of molecular superexcited states journal May 1999
Neutral photodissociation of O2 Rydberg states accompanied by changes of the Rydberg electron's quantum numbers n and l journal March 2000
Dissociative recombination journal August 2006
Attosecond coupled electron and nuclear dynamics in dissociative ionization of H2 journal April 2018
Vector correlations in dissociative photoionization of O2 in the 20–28 eV range. I. Electron-ion kinetic energy correlations journal April 2001
New Rydberg Series in Molecular Oxygen near 500 Å journal June 1965
Two-dimensional charged particle image inversion using a polar basis function expansion journal November 2004
High resolution study of photoionization processes in O 2   journal June 1975
A new, optically forbidden Rydberg series in O 2 converging to the O + 2 c   4 Σ − u  limit journal June 1981
O + 2 ions dissociation studied by threshold photoelectron–photoion coincidence method journal May 1985
A graphical unitary group approach to study multiplet specific multichannel electron correlation effects in the photoionization of O 2 journal June 1995
Multiplet‐specific multichannel electron‐correlation effects in the photoionization of NO journal June 1996
Ultrafast decay of superexcited cΣu−4nlσgv=0,1 states of O 2 probed with femtosecond photoelectron spectroscopy journal June 2012
High-resolution pulsed field ionization photoelectron study of O2: Predissociation lifetimes and high-n Rydberg lifetimes converging to O2+(c 4Σu−, v+=0,1) journal July 1998
New insights onto dissociation of state-selected O 2 + ions investigated by double imaging photoelectron photoion coincidence: The superimposed 3 2 Π u and c 4 Σ u − inner-valence states journal March 2018
Accurate theoretical spectroscopic investigations of the 20 Λ-S and 58 Ω states of O 2 + cation including the spin–orbit coupling effect journal August 2014
What are the basic mechanisms of electronic transitions in molecular dynamic processes? journal April 1991
Dissociation processes of O 2 in the VUV region 500-700 AA journal June 1985
Photoionisation mass spectrometry of O 2 in the VUV region journal September 1986
Visible and VUV fluorescence from synchrotron radiation induced photoionization and photodissociation of molecular oxygen journal March 1994
The production of autoionizing states of atomic oxygen by the photodissociation of O 2 journal September 1991
High resolution threshold photoelectron and photoion spectroscopy of oxygen in the 12-50 eV photon range journal August 1994
De-excitation dynamics of Rydberg states in O 2 : I. Total cross sections for O I fluorescence emission following predissociation of 2σ -1 u (c 4 Σ - u ) n σ g 3 Σ - u states journal February 2002
Competition between autoionization and dissociation in the [O 2 + (B 2   g   )] nl and [O 2 + (c 4   u   )] nl Rydberg states investigated by photon-induced dissociation to neutral fragments journal October 2003
De-excitation dynamics of Rydberg states in O 2 : II. Vibrational and rotational structure of 2σ −1 u ( c 4 Σ − u )( n s/ n d)σ g 3 Σ − u ( v = 0, 1) states journal November 2004
An angle-resolved dissociative photoionization study of the c 4 Σ − u state in O + 2 using the TPEPICO technique journal July 2010
Effects of Configuration Interaction on Intensities and Phase Shifts journal December 1961
High-resolution inner-valence uv photoelectron spectra of the O 2 molecule and configuration-interaction calculations of Π u 2 states between 20 and 26 eV journal April 1992
Superexcited states of oxygen studied by fast-electron impact journal March 2005
Probing autoionizing states of molecular oxygen with XUV transient absorption: Electronic-symmetry-dependent line shapes and laser-induced modifications journal April 2017
Ultrafast Dynamics of Neutral Superexcited Oxygen: A Direct Measurement of the Competition between Autoionization and Predissociation journal October 2012
Coherent Electron Hole Dynamics Near a Conical Intersection journal September 2014
State-to-State Behavior in the Neutral Dissociation of O 2 Far beyond the Ionization Threshold journal January 1995
Soft X-ray-Driven Femtosecond Molecular Dynamics journal September 2007
Observing the Creation of Electronic Feshbach Resonances in Soft X-ray-Induced O2 Dissociation journal November 2008
Ultrafast electron dynamics in phenylalanine initiated by attosecond pulses journal October 2014
Phase-Matched Generation of Coherent Soft X-rays journal May 1998
Resonant Formation of DNA Strand Breaks by Low-Energy (3 to 20 eV) Electrons journal March 2000
Coherent imaging of an attosecond electron wave packet journal June 2017
Investigation of photoionization and photodissociation of an oxygen molecule by the method of coupled differential equations journal March 2007
Superexcited States of Molecules journal September 1962

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