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State-selective probing of CO2 autoionizing inner valence Rydberg states with attosecond extreme ultraviolet four-wave-mixing spectroscopy

Journal Article · · Physical Review A
 [1];  [2];  [2];  [3];  [2];  [4];  [2]
  1. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States); Princeton Univ., NJ (United States)
  2. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States)
  3. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Davis, CA (United States)
  4. Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division
+ Show Author Affiliations
Nonlinear spectroscopies can disentangle spectra that are congested due to inhomogeneous broadening. Here, in conjunction with theoretical calculations, attosecond extreme ultraviolet (XUV) four-wave-mixing (FWM) spectroscopy is utilized to probe the dynamics of autoionizing inner valence excited Rydberg states of the polyatomic molecule, CO2. This tabletop nonlinear technique employs a short attosecond XUV pulse train and two noncollinear, few-cycle near-infrared pulses to generate background-free XUV wave-mixing signals. FWM emission is observed from the n=5-7 states of the Henning sharp ndσg Rydberg series that converges to the ionic $$\widetilde{B}$$ 2Σ$$^{+}_{u}$$ state. However, these transient emission signals decay with lifetimes of 33 ± 6, 53 ± 2, and 94 ± 2 fs, respectively, which calculations show are consistent with the lifetimes of the short-lived n=6-8 members of the nsσg character Henning diffuse Rydberg series. The oscillator strengths of transitions between states involved in all possible resonant FWM processes are calculated, verifying that the nonlinear spectra are dominated by pathways described by an initial excitation to the diffuse nsσg Rydberg series and emission from the sharp ndσg Rydberg series. The results substantiate not only that attosecond XUV FWM spectroscopy produces rigorous and meaningful measurements of ultrafast dynamics in polyatomic systems, but also that nonlinear spectroscopic techniques are versatile tools to selectively probe dynamics that are otherwise difficult to access.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
USDOE Office of Science (SC), Basic Energy Sciences (BES); USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1974754
Alternate ID(s):
OSTI ID: 1907191
Journal Information:
Physical Review A, Journal Name: Physical Review A Journal Issue: 6 Vol. 106; ISSN 2469-9926
Publisher:
American Physical Society (APS)Copyright Statement
Country of Publication:
United States
Language:
English

References (55)

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
A study of the absolute photoabsorption, photoionisation and photodissociation cross sections and the photoionisation quantum efficiency of carbon dioxide from the ionisation threshold to 345 Å journal September 1995
High resolution UV photoelectron spectroscopy of CO+2, COS+ and CS+2 using supersonic molecular beams journal January 1988
Advances in instrumentation for FEL-based four-wave-mixing experiments
  • Mincigrucci, R.; Foglia, L.; Naumenko, D.
  • Nuclear Instruments and Methods in Physics Research Section A: Accelerators, Spectrometers, Detectors and Associated Equipment, Vol. 907 https://doi.org/10.1016/j.nima.2018.03.051
journal November 2018
Concepts and Methods of 2D Infrared Spectroscopy book January 2011
Two-Dimensional Spectroscopy Is Being Used to Address Core Scientific Questions in Biology and Materials Science journal February 2018
Pathways of Energy Flow in LHCII from Two-Dimensional Electronic Spectroscopy journal November 2009
Relative contributions of greenhouse gas emissions to global warming journal April 1990
Attosecond metrology journal November 2001
Electron localization following attosecond molecular photoionization journal June 2010
Real-time observation of valence electron motion journal August 2010
X-ray and optical wave mixing journal August 2012
Controlling dielectrics with the electric field of light journal December 2012
Four-wave mixing experiments with extreme ultraviolet transient gratings journal April 2015
Water vibrations have strongly mixed intra- and intermolecular character journal September 2013
Direct and simultaneous observation of ultrafast electron and hole dynamics in germanium journal June 2017
Intrinsic homogeneous linewidth and broadening mechanisms of excitons in monolayer transition metal dichalcogenides journal September 2015
Nonlinear XUV signal generation probed by transient grating spectroscopy with attosecond pulses journal March 2019
Extreme-ultraviolet spectral compression by four-wave mixing journal January 2021
Multiple pulse coherent dynamics and wave packet control of the N 2 a′′ 1 Σ+g dark state by attosecond four-wave mixing journal January 2018
Coupled nuclear–electronic decay dynamics of O2 inner valence excited states revealed by attosecond XUV wave-mixing spectroscopy journal January 2021
Pulsed field ionization–photoelectron bands for CO2+(A 2Πu and B 2Σu+) in the energy range of 17.2–19.0 eV: An experimental and theoretical study journal November 2000
Absorption, Photoionization, and Fluorescence of CO2 journal April 1966
Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen journal January 1989
Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions journal May 1992
Selective population of spin–orbit levels in the autoionization of a polyatomic molecule: Branching ratios and asymmetry parameters for the Tanaka–Ogawa Rydberg series in CO2 journal June 1994
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
Photoelectron imaging of XUV photoionization of CO2by 13–40 eV synchrotron radiation journal September 2013
Autoionization dynamics of ( 2 P 1/2 ) ns/d states in krypton probed by noncollinear wave mixing with attosecond extreme ultraviolet and few-cycle near infrared pulses journal September 2019
Universal Gaussian basis sets for an optimum representation of Rydberg and continuum wavefunctions journal July 1989
Asymmetry in the molecular-frame photoelectron angular distribution for oxygen 1s photoemission from CO 2 journal September 2012
Attosecond transient absorption of argon atoms in the vacuum ultraviolet region: line energy shifts versus coherent population transfer journal January 2016
Self-heterodyned detection of dressed state coherences in helium by noncollinear extreme ultraviolet wave mixing with attosecond pulses journal May 2020
Effects of Configuration Interaction on Intensities and Phase Shifts journal December 1961
Nonlinear spectroscopy by multiresonant four-wave mixing journal September 1980
Theoretical study of photoelectron angular distributions in single-photon ionization of aligned N 2 and CO 2 journal March 2010
Near-resonant four-wave mixing of attosecond extreme-ultraviolet pulses with near-infrared pulses in neon: Detection of electronic coherences journal August 2016
Noncollinear wave mixing of attosecond XUV and few-cycle optical laser pulses in gas-phase atoms: Toward multidimensional spectroscopy involving XUV excitations journal November 2016
Excited-state vibronic wave-packet dynamics in H 2 probed by XUV transient four-wave mixing journal February 2018
Solid state core-exciton dynamics in NaCl observed by tabletop attosecond four-wave mixing spectroscopy journal June 2021
Coherent Electron Hole Dynamics Near a Conical Intersection journal September 2014
Selectivity of Electronic Coherence and Attosecond Ionization Delays in Strong-Field Double Ionization journal June 2018
First Evidence of Purely Extreme-Ultraviolet Four-Wave Mixing journal June 2018
High-order harmonic generation from atoms and ions in the high intensity regime journal June 1992
Plasma perspective on strong field multiphoton ionization journal September 1993
Multidimensional spectroscopy with attosecond extreme ultraviolet and shaped near-infrared pulses journal September 2018
Ultrafast electron dynamics in phenylalanine initiated by attosecond pulses journal October 2014
Attosecond band-gap dynamics in silicon journal December 2014
RYDBERG ABSORPTION SERIES OF CO2 CONVERGING TO THE 2Πu STATE OF journal July 1962
Multiresonant Coherent Multidimensional Spectroscopy journal May 2011
Mass-Spectrometric Study of Photoionization VI O_2, CO_2, COS, and CS_2† journal August 1967
Supercontinuum generation by stimulated Raman scattering and parametric four-wave mixing in photonic crystal fibers journal April 2002
Attosecond optics and technology: progress to date and future prospects [Invited] journal January 2016
Generating high-contrast, near single-cycle waveforms with third-order dispersion compensation journal January 2017

Figures / Tables (12)

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Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Rydberg atoms & molecules
attosecond laser spectrometry
autoionization & auger processes
configuration interaction
electronic excitation & ionization
four-wave mixing
high-harmonic generation
laser techniques
light-matter interaction
molecules
nonlinear optics
optical transient phenomena
quantum chemistry methods
single- and few-photon ionization & excitation
ultrafast phenomena