Probing the Dynamics of Rydberg and Valence States of Molecular Nitrogen with Attosecond Transient Absorption Spectroscopy
Abstract
An attosecond pulse is used to create a wavepacket in molecular nitrogen composed of multiple bound and autoionizing electronic states of Rydberg and valence character between 12 and 16.7 eV. A time-delayed, few-femtosecond, near-infrared (NIR) laser pulse is used to couple individual states in the wavepacket to multiple neighboring states, resulting in time-dependent modification of the absorption spectrum and revealing both individual quantum beats of the wavepacket and the energy shifts of the excited states in the presence of the strong NIR field. The broad bandwidth of the attosecond pulse and high energy resolution of the extreme ultraviolet spectrometer allow the simultaneous observation of time-dependent dynamics for many individual vibrational levels in each electronic state. Quantum beating with periods from 1.3 to 12 fs and transient line shape changes are observed among vibrational levels of a progression of electronically autoionizing Rydberg states leading to the excited A2πuN2+ ion core. Vibrational levels in the valence b1πu state exhibit 50 fs oscillation periods, revealing superpositions between individual vibrational levels within this state. Comparisons are made to previous studies of electronic wavepackets in atoms that highlight similarities to atomic behavior yet illustrate unique contributions of the diatomic molecular structure to the wavepacket, includingmore »
- Authors:
-
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
- Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States)
- Publication Date:
- Research Org.:
- Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
- Sponsoring Org.:
- USDOE Office of Science (SC), Basic Energy Sciences (BES)
- OSTI Identifier:
- 1532187
- Grant/Contract Number:
- AC02-05CH11231
- Resource Type:
- Accepted Manuscript
- Journal Name:
- Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
- Additional Journal Information:
- Journal Volume: 120; Journal Issue: 19; Journal ID: ISSN 1089-5639
- Publisher:
- American Chemical Society
- Country of Publication:
- United States
- Language:
- English
- Subject:
- 37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
Citation Formats
Warrick, Erika R., Cao, Wei, Neumark, Daniel M., and Leone, Stephen R. Probing the Dynamics of Rydberg and Valence States of Molecular Nitrogen with Attosecond Transient Absorption Spectroscopy. United States: N. p., 2016.
Web. doi:10.1021/acs.jpca.5b11570.
Warrick, Erika R., Cao, Wei, Neumark, Daniel M., & Leone, Stephen R. Probing the Dynamics of Rydberg and Valence States of Molecular Nitrogen with Attosecond Transient Absorption Spectroscopy. United States. https://doi.org/10.1021/acs.jpca.5b11570
Warrick, Erika R., Cao, Wei, Neumark, Daniel M., and Leone, Stephen R. Wed .
"Probing the Dynamics of Rydberg and Valence States of Molecular Nitrogen with Attosecond Transient Absorption Spectroscopy". United States. https://doi.org/10.1021/acs.jpca.5b11570. https://www.osti.gov/servlets/purl/1532187.
@article{osti_1532187,
title = {Probing the Dynamics of Rydberg and Valence States of Molecular Nitrogen with Attosecond Transient Absorption Spectroscopy},
author = {Warrick, Erika R. and Cao, Wei and Neumark, Daniel M. and Leone, Stephen R.},
abstractNote = {An attosecond pulse is used to create a wavepacket in molecular nitrogen composed of multiple bound and autoionizing electronic states of Rydberg and valence character between 12 and 16.7 eV. A time-delayed, few-femtosecond, near-infrared (NIR) laser pulse is used to couple individual states in the wavepacket to multiple neighboring states, resulting in time-dependent modification of the absorption spectrum and revealing both individual quantum beats of the wavepacket and the energy shifts of the excited states in the presence of the strong NIR field. The broad bandwidth of the attosecond pulse and high energy resolution of the extreme ultraviolet spectrometer allow the simultaneous observation of time-dependent dynamics for many individual vibrational levels in each electronic state. Quantum beating with periods from 1.3 to 12 fs and transient line shape changes are observed among vibrational levels of a progression of electronically autoionizing Rydberg states leading to the excited A2πuN2+ ion core. Vibrational levels in the valence b1πu state exhibit 50 fs oscillation periods, revealing superpositions between individual vibrational levels within this state. Comparisons are made to previous studies of electronic wavepackets in atoms that highlight similarities to atomic behavior yet illustrate unique contributions of the diatomic molecular structure to the wavepacket, including the influence of different electronic potentials and vibrational-level-specific electronic dynamics.},
doi = {10.1021/acs.jpca.5b11570},
journal = {Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory},
number = 19,
volume = 120,
place = {United States},
year = {Wed Feb 10 00:00:00 EST 2016},
month = {Wed Feb 10 00:00:00 EST 2016}
}
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