DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Multiple pulse coherent dynamics and wave packet control of the N2 a" 1 Σ$$^+_g$$ dark state by attosecond four-wave mixing

Abstract

Nonlinear multidimensional spectroscopy is ubiquitous in the optical and radio frequency regions as a powerful tool to access structure and dynamics. The extension of this technique into the extreme ultraviolet (XUV) region with attosecond pulses holds promise for probing electronic dynamics and correlations with unprecedented time and spatial resolution. In this work, we use noncollinear four-wave mixing of a weak XUV attosecond pulse train (11–17 eV) and few-femtosecond NIR pulses (800 nm) to spectroscopically and dynamically probe the dipole-forbidden double-well potential of the a" 1Σ+g electronic state of nitrogen. The results demonstrate optical coupling of the inner and outer limits of the initial XUV-prepared vibrational wave packet in the valence character b' 1Σ+u state to the inner and outer wells, respectively, of the a" 1Σ+g double well state by 800 nm light. Two four-wave mixing schemes with different pulse timing sequences and noncollinear beam geometries are used (one NIR pulse collinear and one NIR pulse noncollinear versus both NIR pulses noncollinear to the XUV beam) to measure the a" dark state energetic structure and to control the dynamical preparation and motion of a dark state wave packet by selective population of either the inner Rydberg or outer valence-character potential well.more » Finally, experimental measurements of the a" 1Σ+g outer well vibrational spacing and anharmonicity closely match the values theoretically predicted for this previously unobserved state.« less

Authors:
ORCiD logo [1]; ORCiD logo [1];  [1];  [2]; ORCiD logo [1]; ORCiD logo [1]
  1. Lawrence Berkeley National Lab. (LBNL), Berkeley, CA (United States); Univ. of California, Berkeley, CA (United States)
  2. 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); National Science Foundation (NSF)
OSTI Identifier:
1580348
Alternate Identifier(s):
OSTI ID: 1471430
Grant/Contract Number:  
AC02-05CH11231
Resource Type:
Accepted Manuscript
Journal Name:
Faraday Discussions
Additional Journal Information:
Journal Volume: 212; Journal Issue: 0; Journal ID: ISSN 1359-6640
Publisher:
Royal Society of Chemistry
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Warrick, Erika R., Fidler, Ashley P., Cao, Wei, Bloch, Etienne, Neumark, Daniel M., and Leone, Stephen R. Multiple pulse coherent dynamics and wave packet control of the N2 a" 1 Σ$^+_g$ dark state by attosecond four-wave mixing. United States: N. p., 2018. Web. doi:10.1039/c8fd00074c.
Warrick, Erika R., Fidler, Ashley P., Cao, Wei, Bloch, Etienne, Neumark, Daniel M., & Leone, Stephen R. Multiple pulse coherent dynamics and wave packet control of the N2 a" 1 Σ$^+_g$ dark state by attosecond four-wave mixing. United States. https://doi.org/10.1039/c8fd00074c
Warrick, Erika R., Fidler, Ashley P., Cao, Wei, Bloch, Etienne, Neumark, Daniel M., and Leone, Stephen R. Tue . "Multiple pulse coherent dynamics and wave packet control of the N2 a" 1 Σ$^+_g$ dark state by attosecond four-wave mixing". United States. https://doi.org/10.1039/c8fd00074c. https://www.osti.gov/servlets/purl/1580348.
@article{osti_1580348,
title = {Multiple pulse coherent dynamics and wave packet control of the N2 a" 1 Σ$^+_g$ dark state by attosecond four-wave mixing},
author = {Warrick, Erika R. and Fidler, Ashley P. and Cao, Wei and Bloch, Etienne and Neumark, Daniel M. and Leone, Stephen R.},
abstractNote = {Nonlinear multidimensional spectroscopy is ubiquitous in the optical and radio frequency regions as a powerful tool to access structure and dynamics. The extension of this technique into the extreme ultraviolet (XUV) region with attosecond pulses holds promise for probing electronic dynamics and correlations with unprecedented time and spatial resolution. In this work, we use noncollinear four-wave mixing of a weak XUV attosecond pulse train (11–17 eV) and few-femtosecond NIR pulses (800 nm) to spectroscopically and dynamically probe the dipole-forbidden double-well potential of the a" 1Σ+g electronic state of nitrogen. The results demonstrate optical coupling of the inner and outer limits of the initial XUV-prepared vibrational wave packet in the valence character b' 1Σ+u state to the inner and outer wells, respectively, of the a" 1Σ+g double well state by 800 nm light. Two four-wave mixing schemes with different pulse timing sequences and noncollinear beam geometries are used (one NIR pulse collinear and one NIR pulse noncollinear versus both NIR pulses noncollinear to the XUV beam) to measure the a" dark state energetic structure and to control the dynamical preparation and motion of a dark state wave packet by selective population of either the inner Rydberg or outer valence-character potential well. Finally, experimental measurements of the a" 1Σ+g outer well vibrational spacing and anharmonicity closely match the values theoretically predicted for this previously unobserved state.},
doi = {10.1039/c8fd00074c},
journal = {Faraday Discussions},
number = 0,
volume = 212,
place = {United States},
year = {Tue May 08 00:00:00 EDT 2018},
month = {Tue May 08 00:00:00 EDT 2018}
}

Journal Article:
Free Publicly Available Full Text
Publisher's Version of Record

Citation Metrics:
Cited by: 19 works
Citation information provided by
Web of Science

Save / Share:

Works referenced in this record:

Time-resolved four-wave-mixing spectroscopy for inner-valence transitions
journal, January 2016

  • Ding, Thomas; Ott, Christian; Kaldun, Andreas
  • Optics Letters, Vol. 41, Issue 4
  • DOI: 10.1364/OL.41.000709

Observation of the y1Πg–c4′1Σ+u and k1Πg–c4′1Σ+u systems of N2
journal, September 1999


New Rydberg-Rydberg transitions in N2. Identification of the d3 1Σg+ state
journal, October 2004

  • Cossart, D.; Cossart-Magos, C.
  • The Journal of Chemical Physics, Vol. 121, Issue 15
  • DOI: 10.1063/1.1791154

Ab initio study of valence-state potential energy curves of nitrogen
journal, April 1982

  • Ermler, W. C.; McLean, A. D.; Mulliken, R. S.
  • The Journal of Physical Chemistry, Vol. 86, Issue 8
  • DOI: 10.1021/j100397a019

A b i n i t i o calculations of potential energy curves and transition moments of 1 Σ + g and 1 Σ + u states of N 2
journal, January 1987

  • Ermler, Walter C.; Clark, Joseph P.; Mulliken, Robert S.
  • The Journal of Chemical Physics, Vol. 86, Issue 1
  • DOI: 10.1063/1.452573

Observation of a Photon Echo
journal, November 1964


Reconstruction of an excited-state molecular wave packet with attosecond transient absorption spectroscopy
journal, August 2016


Coherent pulse sequence induced control of selectivity of reactions: Exact quantum mechanical calculations
journal, November 1986

  • Tannor, David J.; Kosloff, Ronnie; Rice, Stuart A.
  • The Journal of Chemical Physics, Vol. 85, Issue 10
  • DOI: 10.1063/1.451542

Attosecond science in atomic, molecular, and condensed matter physics
journal, January 2016

  • Leone, Stephen R.; Neumark, Daniel M.
  • Faraday Discussions, Vol. 194
  • DOI: 10.1039/C6FD00174B

Spectroscopy above the ionization threshold: Dissociative recombination of the ground vibrational level of N2+
journal, August 2012

  • Guberman, Steven L.
  • The Journal of Chemical Physics, Vol. 137, Issue 7
  • DOI: 10.1063/1.4739472

Excited-state vibronic wave-packet dynamics in H 2 probed by XUV transient four-wave mixing
journal, February 2018


Observation of autoionization dynamics and sub-cycle quantum beating in electronic molecular wave packets
journal, February 2016

  • Reduzzi, M.; Chu, W-C; Feng, C.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 49, Issue 6
  • DOI: 10.1088/0953-4075/49/6/065102

Identification of Two Low‐Lying Non‐Rydberg States of the Nitrogen Molecule
journal, July 1970

  • Michels, H. H.
  • The Journal of Chemical Physics, Vol. 53, Issue 2
  • DOI: 10.1063/1.1674069

Vibrational Anharmonicities Revealed by Coherent Two-Dimensional Infrared Spectroscopy
journal, March 2001


An R-matrix study of singlet and triplet continuum states of N 2
journal, May 2014

  • Little, Duncan A.; Tennyson, Jonathan
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 47, Issue 10
  • DOI: 10.1088/0953-4075/47/10/105204

Optimal Control of Ionization Processes in NaK:  Comparison between Theory and Experiment
journal, May 2004

  • Schäfer-Bung, Boris; Mitrić, Roland; Bonačić-Koutecký, Vlasta
  • The Journal of Physical Chemistry A, Vol. 108, Issue 19
  • DOI: 10.1021/jp049153p

Two-dimensional spectroscopy of a molecular dimer unveils the effects of vibronic coupling on exciton coherences
journal, January 2014

  • Halpin, Alexei; Johnson, Philip J. M.; Tempelaar, Roel
  • Nature Chemistry, Vol. 6, Issue 3
  • DOI: 10.1038/nchem.1834

Highly excited states of gerade symmetry in molecular nitrogen
journal, May 2002

  • de Lange, Arno; Lang, Rüdiger; van der Zande, Wim
  • The Journal of Chemical Physics, Vol. 116, Issue 18
  • DOI: 10.1063/1.1468220

High‐resolution jet absorption study of nitrogen near 800 Å
journal, January 1990

  • Huber, K. P.; Jungen, Ch.
  • The Journal of Chemical Physics, Vol. 92, Issue 2
  • DOI: 10.1063/1.458589

Attosecond transient absorption spectroscopy of molecular nitrogen: Vibrational coherences in the b′ 1Σ+u state
journal, September 2017


Comment on: Two‐photon spectroscopy of N 2 : Multiphoton ionization, laser‐induced fluorescence, and direct absorption via the a ‘  1 Σ + g state
journal, May 1992

  • Vrakking, Marcus J. J.; Bracker, Allan S.; Lee, Yuan T.
  • The Journal of Chemical Physics, Vol. 96, Issue 9
  • DOI: 10.1063/1.462528

Two New Band Systems in the Near Ultraviolet Spectrum of N 2
journal, October 1975

  • Carroll, P. K.; Subbaram, K. V.
  • Canadian Journal of Physics, Vol. 53, Issue 19
  • DOI: 10.1139/p75-266

High-Resolution 2 + 1 REMPI Study of the a′′ 1 Σ g + State in N 2
journal, March 2009

  • Salumbides, E. J.; Khramov, A.; Ubachs, W.
  • The Journal of Physical Chemistry A, Vol. 113, Issue 11
  • DOI: 10.1021/jp808698u

Two‐photon spectroscopy of N 2 : Multiphoton ionization, laser‐induced fluorescence, and direct absorption via the a ‘  1 Σ + g state
journal, August 1991

  • Lykke, Keith R.; Kay, Bruce D.
  • The Journal of Chemical Physics, Vol. 95, Issue 4
  • DOI: 10.1063/1.460981

Complete Reconstruction of the Wave Function of a Reacting Molecule by Four-Wave Mixing Spectroscopy
journal, April 2011


Role of Excited Core Rydberg States in Dissociative Recombination
journal, November 2007

  • Guberman, Steven L.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 44
  • DOI: 10.1021/jp070892q

Valence–Rydberg electronic states of N 2 : spectroscopy and spin–orbit couplings
journal, November 2010

  • Hochlaf, M.; Ndome, H.; Hammoutène, D.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 43, Issue 24
  • DOI: 10.1088/0953-4075/43/24/245101

Probing the Dynamics of Rydberg and Valence States of Molecular Nitrogen with Attosecond Transient Absorption Spectroscopy
journal, February 2016

  • Warrick, Erika R.; Cao, Wei; Neumark, Daniel M.
  • The Journal of Physical Chemistry A, Vol. 120, Issue 19
  • DOI: 10.1021/acs.jpca.5b11570

Multidimensional Attosecond Resonant X-Ray Spectroscopy of Molecules: Lessons from the Optical Regime
journal, April 2013


(2+1)REMPI on molecular nitrogen through the 1 Σ g + (II)-state
journal, February 2007


High-resolution threshold photoelectron and photoion spectroscopy of molecular nitrogen in the 15.0–52.7 eV photon energy range
journal, August 2014

  • Yencha, Andrew J.; Ellis, Kate; King, George C.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 195
  • DOI: 10.1016/j.elspec.2014.07.004

Measurement of the lifetime of the metastable a ’’ Σ g + 1 state of N 2
journal, April 1991


Double Optical Gating of High-Order Harmonic Generation with Carrier-Envelope Phase Stabilized Lasers
journal, March 2008


Two-Quantum 2D FT Electronic Spectroscopy of Biexcitons in GaAs Quantum Wells
journal, May 2009


Vibrational transitions in excited states of molecules using coherent stokes raman spectroscopy: application to ferrocytochrome-C
journal, November 1981


Nonlinear Spectroscopy
journal, October 1978


High resolution absorption studies of the b 1 Π u  ←  X 1 Σ g + system of nitrogen
journal, March 1969

  • Carroll, P. K.; Collins, C. P.
  • Canadian Journal of Physics, Vol. 47, Issue 5
  • DOI: 10.1139/p69-073

Femtosecond pump–probe photoelectron spectroscopy on Na2: a tool to study basic coherent control schemes
journal, September 2000


Femtosecond transient-grating techniques: Population and coherence dynamics involving ground and excited states
journal, March 1999

  • Brown, Emily J.; Zhang, Qingguo; Dantus, Marcos
  • The Journal of Chemical Physics, Vol. 110, Issue 12, p. 5772-5788
  • DOI: 10.1063/1.478476

Coherent pulse sequence induced control of selectivity of reactions. Exact quantum-mechanical calculations
journal, January 1986

  • Rice, Stuart A.; Tannor, David J.; Kosloff, Ronnie
  • Journal of the Chemical Society, Faraday Transactions 2, Vol. 82, Issue 12
  • DOI: 10.1039/f29868202423

Nonlinear Spectroscopy
journal, October 1972


Vibrational Anharmonicities Revealed by Coherent Two-Dimensional Infrared Spectroscopy
text, January 2001


Time-resolved four-wave-mixing spectroscopy for inner-valence transitions
text, January 2015


Works referencing / citing this record:

Nonlinear XUV signal generation probed by transient grating spectroscopy with attosecond pulses
journal, March 2019


Tracking attosecond electronic coherences using phase-manipulated extreme ultraviolet pulses
journal, February 2020


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

  • Fidler, Ashley P.; Marroux, Hugo J. B.; Warrick, Erika R.
  • The Journal of Chemical Physics, Vol. 151, Issue 11
  • DOI: 10.1063/1.5113912

Transient absorption spectroscopy using high harmonic generation: a review of ultrafast X-ray dynamics in molecules and solids
journal, April 2019

  • Geneaux, Romain; Marroux, Hugo J. B.; Guggenmos, Alexander
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 377, Issue 2145
  • DOI: 10.1098/rsta.2017.0463

Tracking attosecond electronic coherences using phase-manipulated extreme ultraviolet pulses
text, January 2020

  • Wituschek, Andreas; Bruder, Lukas; Allaria, Enrico
  • Deutsches Elektronen-Synchrotron, DESY, Hamburg
  • DOI: 10.3204/pubdb-2020-01741

Tracking Attosecond Electronic Coherences Using Phase-Manipulated Extreme Ultraviolet Pulses
text, January 2019