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Title: A theoretical and experimental benchmark study of core-excited states in nitrogen

Abstract

The high resolution near edge X-ray absorption fine structure spectrum of nitrogen displays the vibrational structure of the core-excited states. This makes nitrogen well suited for assessing the accuracy of different electronic structure methods for core excitations. We report high resolution experimental measurements performed at the SOLEIL synchrotron facility. These are compared with theoretical spectra calculated using coupled cluster theory and algebraic diagrammatic construction theory. The coupled cluster singles and doubles with perturbative triples model known as CC3 is shown to accurately reproduce the experimental excitation energies as well as the spacing of the vibrational transitions. In conclusion, the computational results are also shown to be systematically improved within the coupled cluster hierarchy, with the coupled cluster singles, doubles, triples, and quadruples method faithfully reproducing the experimental vibrational structure.

Authors:
 [1]; ORCiD logo [2]; ORCiD logo [3];  [4]; ORCiD logo [5];  [6]; ORCiD logo [7]
  1. Univ. of Oslo (Norway). Hylleraas Centre for Quantum Molecular Sciences, Dept. of Chemistry; Norwegian Univ. of Science and Technology, Trondheim (Norway). Dept. of Chemistry; SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Stanford Univ., CA (United States). Dept. of Chemistry
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE)
  3. Johns Hopkins Univ., Baltimore, MD (United States). Department of Chemistry
  4. Synchrotron SOLEIL, Saint-Aubin, Gif-sur-Yvette Cedex (France); Lund Univ. (Sweden). Dept. of Physics
  5. Technical Univ. of Denmark, Lyngby (Denmark). Dept. of Chemistry; Aarhus Univ. (Denmark). Aarhus Inst. of Advanced Studies
  6. SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Univ. of Potsdam, Potsdam (Germany). Dept. of Physics and Astronomy
  7. Norwegian Univ. of Science and Technology, Trondheim (Norway). Dept. of Chemistry; SLAC National Accelerator Lab., Menlo Park, CA (United States). Photon Ultrafast Laser Science and Engineering Inst. (PULSE); Stanford Univ., CA (United States). Dept. of Chemistry
Publication Date:
Research Org.:
SLAC National Accelerator Laboratory (SLAC), Menlo Park, CA (United States)
Sponsoring Org.:
USDOE; German National Academy of Sciences Leopoldina
OSTI Identifier:
1427025
Grant/Contract Number:  
AC02-76SF00515; 639508; 609033
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 148; Journal Issue: 6; Journal ID: ISSN 0021-9606
Publisher:
American Institute of Physics (AIP)
Country of Publication:
United States
Language:
English
Subject:
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY

Citation Formats

Myhre, Rolf H., Wolf, Thomas J. A., Cheng, Lan, Nandi, Saikat, Coriani, Sonia, Gühr, Markus, and Koch, Henrik. A theoretical and experimental benchmark study of core-excited states in nitrogen. United States: N. p., 2018. Web. doi:10.1063/1.5011148.
Myhre, Rolf H., Wolf, Thomas J. A., Cheng, Lan, Nandi, Saikat, Coriani, Sonia, Gühr, Markus, & Koch, Henrik. A theoretical and experimental benchmark study of core-excited states in nitrogen. United States. https://doi.org/10.1063/1.5011148
Myhre, Rolf H., Wolf, Thomas J. A., Cheng, Lan, Nandi, Saikat, Coriani, Sonia, Gühr, Markus, and Koch, Henrik. Wed . "A theoretical and experimental benchmark study of core-excited states in nitrogen". United States. https://doi.org/10.1063/1.5011148. https://www.osti.gov/servlets/purl/1427025.
@article{osti_1427025,
title = {A theoretical and experimental benchmark study of core-excited states in nitrogen},
author = {Myhre, Rolf H. and Wolf, Thomas J. A. and Cheng, Lan and Nandi, Saikat and Coriani, Sonia and Gühr, Markus and Koch, Henrik},
abstractNote = {The high resolution near edge X-ray absorption fine structure spectrum of nitrogen displays the vibrational structure of the core-excited states. This makes nitrogen well suited for assessing the accuracy of different electronic structure methods for core excitations. We report high resolution experimental measurements performed at the SOLEIL synchrotron facility. These are compared with theoretical spectra calculated using coupled cluster theory and algebraic diagrammatic construction theory. The coupled cluster singles and doubles with perturbative triples model known as CC3 is shown to accurately reproduce the experimental excitation energies as well as the spacing of the vibrational transitions. In conclusion, the computational results are also shown to be systematically improved within the coupled cluster hierarchy, with the coupled cluster singles, doubles, triples, and quadruples method faithfully reproducing the experimental vibrational structure.},
doi = {10.1063/1.5011148},
journal = {Journal of Chemical Physics},
number = 6,
volume = 148,
place = {United States},
year = {2018},
month = {2}
}

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Cited by: 24 works
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Figures / Tables:

Figure 1 Figure 1: Comparison of CC3 and experiment for the four lowest excited states. The intensity of the first peak is normalized to 1 and empirical line broadening added to the theoretical spectrum.

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Works referenced in this record:

Calculating X-ray Absorption Spectra of Open-Shell Molecules with the Unrestricted Algebraic-Diagrammatic Construction Scheme for the Polarization Propagator
journal, September 2014

  • Wenzel, Jan; Wormit, Michael; Dreuw, Andreas
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 10
  • DOI: 10.1021/ct5006888

Inner-shell photoionization and core-hole decay of Xe and XeF2
journal, June 2015

  • Southworth, Stephen H.; Wehlitz, Ralf; Picón, Antonio
  • The Journal of Chemical Physics, Vol. 142, Issue 22
  • DOI: 10.1063/1.4922208

C 1s near edge X-ray absorption fine structure (NEXAFS) of substituted benzoic acids—A theoretical and experimental study
journal, February 2007

  • Bâldea, I.; Schimmelpfennig, B.; Plaschke, M.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 154, Issue 3
  • DOI: 10.1016/j.elspec.2006.12.024

NEXAFS Spectroscopy
book, January 1992


Coupled cluster response functions
journal, September 1990

  • Koch, Henrik; Jo/rgensen, Poul
  • The Journal of Chemical Physics, Vol. 93, Issue 5
  • DOI: 10.1063/1.458814

Time-resolved x-ray absorption spectroscopy with a water window high-harmonic source
journal, January 2017


Coupled cluster response functions revisited
journal, May 1997

  • Pedersen, Thomas Bondo; Koch, Henrik
  • The Journal of Chemical Physics, Vol. 106, Issue 19
  • DOI: 10.1063/1.473814

Communication: X-ray absorption spectra and core-ionization potentials within a core-valence separated coupled cluster framework
journal, November 2015

  • Coriani, Sonia; Koch, Henrik
  • The Journal of Chemical Physics, Vol. 143, Issue 18
  • DOI: 10.1063/1.4935712

New set-up for high-quality soft-X-ray absorption spectroscopy of large organic molecules in the gas phase
journal, November 2011

  • Holch, Florian; Hübner, Dominique; Fink, Rainer
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 184, Issue 8-10
  • DOI: 10.1016/j.elspec.2011.05.006

The multilevel CC3 coupled cluster model
journal, July 2016

  • Myhre, Rolf H.; Koch, Henrik
  • The Journal of Chemical Physics, Vol. 145, Issue 4
  • DOI: 10.1063/1.4959373

Nuclear quantum effects in the structure and lineshapes of the N2 near-edge x-ray absorption fine structure spectrum
journal, March 2010

  • Fatehi, Shervin; Schwartz, Craig P.; Saykally, Richard J.
  • The Journal of Chemical Physics, Vol. 132, Issue 9
  • DOI: 10.1063/1.3324889

Coupled-cluster response theory for near-edge x-ray-absorption fine structure of atoms and molecules
journal, February 2012


Theoretical core-level excitation spectra of N 2 and CO by a new polarisation propagator method
journal, March 1985


The Dalton quantum chemistry program system: The Dalton program
journal, September 2013

  • Aidas, Kestutis; Angeli, Celestino; Bak, Keld L.
  • Wiley Interdisciplinary Reviews: Computational Molecular Science, Vol. 4, Issue 3
  • DOI: 10.1002/wcms.1172

Determination of the electronic and structural configuration of coordination compounds by synchrotron-radiation techniques
journal, October 2014

  • Garino, Claudio; Borfecchia, Elisa; Gobetto, Roberto
  • Coordination Chemistry Reviews, Vol. 277-278
  • DOI: 10.1016/j.ccr.2014.03.027

Electron affinities of the first‐row atoms revisited. Systematic basis sets and wave functions
journal, May 1992

  • Kendall, Rick A.; Dunning, Thom H.; Harrison, Robert J.
  • The Journal of Chemical Physics, Vol. 96, Issue 9
  • DOI: 10.1063/1.462569

Benchmarking Coupled Cluster Methods on Valence Singlet Excited States
journal, July 2014

  • Kánnár, Dániel; Szalay, Péter G.
  • Journal of Chemical Theory and Computation, Vol. 10, Issue 9
  • DOI: 10.1021/ct500495n

An iteration method for the solution of the eigenvalue problem of linear differential and integral operators
journal, October 1950

  • Lanczos, C.
  • Journal of Research of the National Bureau of Standards, Vol. 45, Issue 4
  • DOI: 10.6028/jres.045.026

0.5-keV Soft X-ray attosecond continua
journal, May 2016

  • Teichmann, S. M.; Silva, F.; Cousin, S. L.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11493

Rovibrationally averaged nuclear magnetic shielding tensors calculated at the coupled‐cluster level
journal, December 1996

  • Sundholm, Dage; Gauss, Jürgen; Schäfer, Ansgar
  • The Journal of Chemical Physics, Vol. 105, Issue 24
  • DOI: 10.1063/1.472905

Advances in molecular quantum chemistry contained in the Q-Chem 4 program package
journal, September 2014


Probing ultrafast ππ*/nπ* internal conversion in organic chromophores via K-edge resonant absorption
journal, June 2017


Hetero-site-specific X-ray pump-probe spectroscopy for femtosecond intramolecular dynamics
journal, May 2016

  • Picón, A.; Lehmann, C. S.; Bostedt, C.
  • Nature Communications, Vol. 7, Issue 1
  • DOI: 10.1038/ncomms11652

The CC3 model: An iterative coupled cluster approach including connected triples
journal, February 1997

  • Koch, Henrik; Christiansen, Ove; Jo/rgensen, Poul
  • The Journal of Chemical Physics, Vol. 106, Issue 5
  • DOI: 10.1063/1.473322

Photoinduced Structural Dynamics of Molecular Systems Mapped by Time-Resolved X-ray Methods
journal, May 2017


Exact two-component Hamiltonians revisited
journal, July 2009

  • Liu, Wenjian; Peng, Daoling
  • The Journal of Chemical Physics, Vol. 131, Issue 3
  • DOI: 10.1063/1.3159445

Multireference Nature of Chemistry: The Coupled-Cluster View
journal, December 2011

  • Lyakh, Dmitry I.; Musiał, Monika; Lotrich, Victor F.
  • Chemical Reviews, Vol. 112, Issue 1
  • DOI: 10.1021/cr2001417

An X-ray absorption study of glycine, methionine and proline
journal, March 2007

  • Plekan, O.; Feyer, V.; Richter, R.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 155, Issue 1-3
  • DOI: 10.1016/j.elspec.2006.11.004

Tautomerism in Cytosine and Uracil: A Theoretical and Experimental X-ray Absorption and Resonant Auger Study
journal, September 2010

  • Feyer, Vitaliy; Plekan, Oksana; Richter, Robert
  • The Journal of Physical Chemistry A, Vol. 114, Issue 37
  • DOI: 10.1021/jp105062c

Bright Coherent Ultrahigh Harmonics in the keV X-ray Regime from Mid-Infrared Femtosecond Lasers
journal, June 2012


Gaussian basis sets for use in correlated molecular calculations. V. Core‐valence basis sets for boron through neon
journal, September 1995

  • Woon, David E.; Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 103, Issue 11
  • DOI: 10.1063/1.470645

Many-body theory of core holes
journal, July 1980


Non-orthogonal spin-adaptation of coupled cluster methods: A new implementation of methods including quadruple excitations
journal, February 2015

  • Matthews, Devin A.; Stanton, John F.
  • The Journal of Chemical Physics, Vol. 142, Issue 6
  • DOI: 10.1063/1.4907278

Femtosecond x-ray spectroscopy of an electrocyclic ring-opening reaction
journal, April 2017

  • Attar, Andrew R.; Bhattacherjee, Aditi; Pemmaraju, C. D.
  • Science, Vol. 356, Issue 6333
  • DOI: 10.1126/science.aaj2198

Investigating excited electronic states using the algebraic diagrammatic construction (ADC) approach of the polarisation propagator
journal, February 2014


Asymmetric-Lanczos-Chain-Driven Implementation of Electronic Resonance Convergent Coupled-Cluster Linear Response Theory
journal, April 2012

  • Coriani, Sonia; Fransson, Thomas; Christiansen, Ove
  • Journal of Chemical Theory and Computation, Vol. 8, Issue 5
  • DOI: 10.1021/ct200919e

Ultrafast Probing of Core Hole Localization in N2
journal, May 2008


The iterative calculation of a few of the lowest eigenvalues and corresponding eigenvectors of large real-symmetric matrices
journal, January 1975


Imaging molecular potentials using ultrahigh-resolution resonant photoemission
journal, November 2011

  • Miron, Catalin; Nicolas, Christophe; Travnikova, Oksana
  • Nature Physics, Vol. 8, Issue 2
  • DOI: 10.1038/nphys2159

Communication: An accurate calculation of the S1 C2H2 cis-trans isomerization barrier height
journal, March 2016

  • Baraban, Joshua H.; Matthews, Devin A.; Stanton, John F.
  • The Journal of Chemical Physics, Vol. 144, Issue 11
  • DOI: 10.1063/1.4943865

Psychiatric pharmacotherapy during pregnancy and lactation: The obstetrical point of view
journal, August 2014


Works referencing / citing this record:

An efficient first principles method for molecular pump-probe NEXAFS spectra: Application to thymine and azobenzene
journal, October 2018

  • Ehlert, Christopher; Gühr, Markus; Saalfrank, Peter
  • The Journal of Chemical Physics, Vol. 149, Issue 14
  • DOI: 10.1063/1.5050488

Coupled cluster study of the x-ray absorption spectra of formaldehyde derivatives at the oxygen, carbon, and fluorine K-edges
journal, August 2019

  • Frati, Federica; de Groot, Frank; Cerezo, Javier
  • The Journal of Chemical Physics, Vol. 151, Issue 6
  • DOI: 10.1063/1.5097650