State-selective probing of CO 2 autoionizing inner valence Rydberg states with attosecond extreme ultraviolet four-wave-mixing spectroscopy
Abstract
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.
- Authors:
-
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States); Princeton Univ., NJ (United States)
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Berkeley, CA (United States)
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division; Univ. of California, Davis, CA (United States)
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States). Chemical Sciences Division
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division (CSGB); USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1974754
- Alternate Identifier(s):
- OSTI ID: 1907191
- Grant/Contract Number:
- AC02-05CH11231; BES-ERCAP0020143; DEAC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Physical Review A
- Additional Journal Information:
- Journal Volume: 106; Journal Issue: 6; 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; autoionization & auger processes; electronic excitation & ionization; light-matter interaction; nonlinear optics; optical transient phenomena; single- and few-photon ionization & excitation; ultrafast phenomena; molecules; Rydberg atoms & molecules; attosecond laser spectrometry; configuration interaction; four-wave mixing; high-harmonic generation; laser techniques; quantum chemistry methods
Citation Formats
Fidler, Ashley P., Lin, Yen-Cheng, Gaynor, James D., McCurdy, C. William, Leone, Stephen R., Lucchese, Robert R., and Neumark, Daniel M. State-selective probing of CO2 autoionizing inner valence Rydberg states with attosecond extreme ultraviolet four-wave-mixing spectroscopy. United States: N. p., 2022.
Web. doi:10.1103/physreva.106.063525.
Fidler, Ashley P., Lin, Yen-Cheng, Gaynor, James D., McCurdy, C. William, Leone, Stephen R., Lucchese, Robert R., & Neumark, Daniel M. State-selective probing of CO2 autoionizing inner valence Rydberg states with attosecond extreme ultraviolet four-wave-mixing spectroscopy. United States. https://doi.org/10.1103/physreva.106.063525
Fidler, Ashley P., Lin, Yen-Cheng, Gaynor, James D., McCurdy, C. William, Leone, Stephen R., Lucchese, Robert R., and Neumark, Daniel M. Fri .
"State-selective probing of CO2 autoionizing inner valence Rydberg states with attosecond extreme ultraviolet four-wave-mixing spectroscopy". United States. https://doi.org/10.1103/physreva.106.063525. https://www.osti.gov/servlets/purl/1974754.
@article{osti_1974754,
title = {State-selective probing of CO2 autoionizing inner valence Rydberg states with attosecond extreme ultraviolet four-wave-mixing spectroscopy},
author = {Fidler, Ashley P. and Lin, Yen-Cheng and Gaynor, James D. and McCurdy, C. William and Leone, Stephen R. and Lucchese, Robert R. and Neumark, Daniel M.},
abstractNote = {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.},
doi = {10.1103/physreva.106.063525},
journal = {Physical Review A},
number = 6,
volume = 106,
place = {United States},
year = {Fri Dec 30 00:00:00 EST 2022},
month = {Fri Dec 30 00:00:00 EST 2022}
}
Figures / Tables:
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