Title: 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 ndσ_g 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 nsσ_g 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 nsσ_g Rydberg series and emission from the sharp ndσ_g 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:

Fidler, Ashley P.  ^[1];

• Search DOE PAGES for author "Fidler, Ashley P."
• Search DOE PAGES for ORCID "0000-0001-6539-2904"

Lin, Yen-Cheng  ^[2];

• Search DOE PAGES for author "Lin, Yen-Cheng"
• Search DOE PAGES for ORCID "0000-0002-0163-9776"

Gaynor, James D. ^[2]; McCurdy, C. William ^[3]; Leone, Stephen R.  ^[2];

• Search DOE PAGES for author "Leone, Stephen R."
• Search DOE PAGES for ORCID "0000-0003-1819-1338"

Lucchese, Robert R.  ^[4];

• Search DOE PAGES for author "Lucchese, Robert R."
• Search DOE PAGES for ORCID "0000-0002-7200-3775"

Neumark, Daniel M. ^[2]

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+ Show Author Affiliations

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

Publication Date:

Fri Dec 30 00:00:00 EST 2022

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