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

Abstract

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$$_2^+$$c 4Σ$$_u^-$$, 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 4 p excited atomic oxygen fragment, which is not an expected dissociation product of the (O$$_2^+$$c 4Σ$$_u^-$$) nlσ g Rydberg series. Analysis of the time-dependent photoelectron spectra and photoionization calculations indicate that this fragment results from a previously unexplored (O$$_2^+$$ 4II$$_g$$)4 p 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.

Authors:
 [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)
Publication Date:
Research Org.:
Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
Sponsoring Org.:
USDOE Office of Science (SC), Basic Energy Sciences (BES) (SC-22). Chemical Sciences, Geosciences & Biosciences Division; USDOE
OSTI Identifier:
1542413
Alternate Identifier(s):
OSTI ID: 1546301
Grant/Contract Number:  
AC02-05CH11231; SC0018251
Resource Type:
Accepted Manuscript
Journal Name:
Physical Review A
Additional Journal Information:
Journal Volume: 99; Journal Issue: 6; Journal ID: ISSN 2469-9926
Publisher:
American Physical Society (APS)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS

Citation Formats

Plunkett, Alexander, Harkema, Nathan, Lucchese, Robert R., McCurdy, C. William, and Sandhu, Arvinder. Ultrafast Rydberg-state dissociation in oxygen: Identifying the role of multielectron excitations. United States: N. p., 2019. Web. doi:10.1103/PhysRevA.99.063403.
Plunkett, Alexander, Harkema, Nathan, Lucchese, Robert R., McCurdy, C. William, & Sandhu, Arvinder. Ultrafast Rydberg-state dissociation in oxygen: Identifying the role of multielectron excitations. United States. doi:10.1103/PhysRevA.99.063403.
Plunkett, Alexander, Harkema, Nathan, Lucchese, Robert R., McCurdy, C. William, and Sandhu, Arvinder. Thu . "Ultrafast Rydberg-state dissociation in oxygen: Identifying the role of multielectron excitations". United States. doi:10.1103/PhysRevA.99.063403.
@article{osti_1542413,
title = {Ultrafast Rydberg-state dissociation in oxygen: Identifying the role of multielectron excitations},
author = {Plunkett, Alexander and Harkema, Nathan and Lucchese, Robert R. and McCurdy, C. William and Sandhu, Arvinder},
abstractNote = {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.},
doi = {10.1103/PhysRevA.99.063403},
journal = {Physical Review A},
number = 6,
volume = 99,
place = {United States},
year = {2019},
month = {6}
}

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