skip to main content
DOE PAGES title logo U.S. Department of Energy
Office of Scientific and Technical Information

Title: Normal and resonant Auger spectroscopy of isocyanic acid, HNCO

Abstract

In this study, we investigate HNCO by resonant and nonresonant Auger electron spectroscopy at the K-edges of carbon, nitrogen, and oxygen, employing soft X-ray synchrotron radiation. In comparison with the isosteric but linear CO 2 molecule, spectra of the bent HNCO molecule are similar but more complex due to its reduced symmetry, wherein the degeneracy of the π-orbitals is lifted. Resonant Auger electron spectra are presented at different photon energies over the first core-excited 1s → 10a' resonance. All Auger electron spectra are assigned based on ab initio configuration interaction computations combined with the one-center approximation for Auger intensities and moment theory to consider vibrational motion. The calculated spectra were scaled by a newly introduced energy scaling factor, and generally, good agreement is found between experiment and theory for normal as well as resonant Auger electron spectra. A comparison of resonant Auger spectra with nonresonant Auger structures shows a slight broadening as well as a shift of the former spectra between –8 and –9 eV due to the spectating electron. Since HNCO is a small molecule and contains the four most abundant atoms of organic molecules, the reported Auger electron decay spectra will provide a benchmark for further theoretical approachesmore » in the computation of core electron spectra.« less

Authors:
ORCiD logo [1]; ORCiD logo [2]; ORCiD logo [3]; ORCiD logo [4];  [5];  [6];  [5]; ORCiD logo [4];  [7]; ORCiD logo [3]
  1. Univ. Paris-Sud, Univ. Paris-Saclay, Orsay (France); Synchrotron SOLEIL, Gif-sur-Yvette (France); Univ. Wurzburg, Wurzburg (Germany)
  2. SLAC National Accelerator Lab., Menlo Park, CA (United States)
  3. Univ. Tubingen, Tubingen (Germany)
  4. Univ. Wurzburg, Wurzburg (Germany)
  5. Synchrotron SOLEIL, Gif-sur-Yvette (France)
  6. Lund Univ., Lund (Sweden); Synchrotron SOLEIL, Gif-sur-Yvette (France)
  7. Institut fur Physik und Astronomie Univ. Potsdam, Potsdam (Germany)
Publication Date:
Research Org.:
SLAC National Accelerator Lab., Menlo Park, CA (United States)
Sponsoring Org.:
USDOE
OSTI Identifier:
1463389
Alternate Identifier(s):
OSTI ID: 1460916
Grant/Contract Number:  
AC02-76SF00515; FI 575/13-1; FI 575/7-3; SC0012376
Resource Type:
Accepted Manuscript
Journal Name:
Journal of Chemical Physics
Additional Journal Information:
Journal Volume: 149; Journal Issue: 3; 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

Holzmeier, Fabian, Wolf, T. J. A., Gienger, C., Wagner, I., Bozek, J., Nandi, S., Nicolas, C., Fischer, I., Guhr, M., and Fink, Reinhold F. Normal and resonant Auger spectroscopy of isocyanic acid, HNCO. United States: N. p., 2018. Web. doi:10.1063/1.5030621.
Holzmeier, Fabian, Wolf, T. J. A., Gienger, C., Wagner, I., Bozek, J., Nandi, S., Nicolas, C., Fischer, I., Guhr, M., & Fink, Reinhold F. Normal and resonant Auger spectroscopy of isocyanic acid, HNCO. United States. doi:10.1063/1.5030621.
Holzmeier, Fabian, Wolf, T. J. A., Gienger, C., Wagner, I., Bozek, J., Nandi, S., Nicolas, C., Fischer, I., Guhr, M., and Fink, Reinhold F. Thu . "Normal and resonant Auger spectroscopy of isocyanic acid, HNCO". United States. doi:10.1063/1.5030621. https://www.osti.gov/servlets/purl/1463389.
@article{osti_1463389,
title = {Normal and resonant Auger spectroscopy of isocyanic acid, HNCO},
author = {Holzmeier, Fabian and Wolf, T. J. A. and Gienger, C. and Wagner, I. and Bozek, J. and Nandi, S. and Nicolas, C. and Fischer, I. and Guhr, M. and Fink, Reinhold F.},
abstractNote = {In this study, we investigate HNCO by resonant and nonresonant Auger electron spectroscopy at the K-edges of carbon, nitrogen, and oxygen, employing soft X-ray synchrotron radiation. In comparison with the isosteric but linear CO2 molecule, spectra of the bent HNCO molecule are similar but more complex due to its reduced symmetry, wherein the degeneracy of the π-orbitals is lifted. Resonant Auger electron spectra are presented at different photon energies over the first core-excited 1s → 10a' resonance. All Auger electron spectra are assigned based on ab initio configuration interaction computations combined with the one-center approximation for Auger intensities and moment theory to consider vibrational motion. The calculated spectra were scaled by a newly introduced energy scaling factor, and generally, good agreement is found between experiment and theory for normal as well as resonant Auger electron spectra. A comparison of resonant Auger spectra with nonresonant Auger structures shows a slight broadening as well as a shift of the former spectra between –8 and –9 eV due to the spectating electron. Since HNCO is a small molecule and contains the four most abundant atoms of organic molecules, the reported Auger electron decay spectra will provide a benchmark for further theoretical approaches in the computation of core electron spectra.},
doi = {10.1063/1.5030621},
journal = {Journal of Chemical Physics},
number = 3,
volume = 149,
place = {United States},
year = {2018},
month = {7}
}

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

Citation Metrics:
Cited by: 1 work
Citation information provided by
Web of Science

Figures / Tables:

FIG. 1 FIG. 1: Computed molecular orbitals for HNCO (view along the y axis). The bent geometry of the molecule is shown in the xy-symmetry-plane in the indent at the right bottom.

Save / Share:

Works referenced in this record:

Nuclear motion in the O 1s−12πu core-excited states of CO2 probed by sub-natural-width resonant Auger emission spectroscopy
journal, November 2000


Deexcitation electron spectroscopy of core‐excited O 2
journal, June 1990

  • Carroll, T. X.; Thomas, T. D.
  • The Journal of Chemical Physics, Vol. 92, Issue 12
  • DOI: 10.1063/1.458256

A reexamination of the RapreNOx process
journal, December 1990


Competition between Direct and Indirect Dissociation Pathways in Ultraviolet Photodissociation of HNCO
journal, March 2013

  • Yu, Shengrui; Su, Shu; Dorenkamp, Yvonne
  • The Journal of Physical Chemistry A, Vol. 117, Issue 46
  • DOI: 10.1021/jp312793k

Effects of time evolution of coherently excited vibrations in molecular core—hole decay spectra of O2
journal, September 1993


Near threshold excitation of K V V Auger spectra in carbon monoxide using electron–electron coincidence spectroscopy
journal, April 1985

  • Ungier, L.; Thomas, T. D.
  • The Journal of Chemical Physics, Vol. 82, Issue 7
  • DOI: 10.1063/1.448212

The H–NCO bond energy and Δ H 0 f (NCO) from photoionization mass spectrometric studies of HNCO and NCO
journal, March 1994

  • Ruscic, B.; Berkowitz, J.
  • The Journal of Chemical Physics, Vol. 100, Issue 6
  • DOI: 10.1063/1.466281

Photoexcitation and Auger decay of the Renner-Teller split C 1 s 1 π u * state in CO 2
journal, August 2000


Symmetry-resolved soft x-ray absorption spectroscopy: its application to simple molecules
journal, May 2005

  • Adachi, Jun-ichi; Kosugi, Nobuhiro; Yagishita, Akira
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 38, Issue 11
  • DOI: 10.1088/0953-4075/38/11/r01

Decay of and OCS after sulphur 1s photoexcitation: I. Total ionic charge spectra and electronic processes
journal, March 1997

  • Esser, B.; Ankerhold, U.; Anders, N.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 30, Issue 5
  • DOI: 10.1088/0953-4075/30/5/014

Decay of and OCS after sulphur 1s photoexcitation: II. Dissociation channels and kinematics
journal, March 1997

  • Ankerhold, U.; Esser, B.; Busch, F. von
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 30, Issue 5
  • DOI: 10.1088/0953-4075/30/5/015

A multi-configuration reference CEPA method based on pair natural orbitals
journal, November 1993

  • Fink, Reinhold; Staemmler, Volker
  • Theoretica Chimica Acta, Vol. 87, Issue 1-2
  • DOI: 10.1007/bf01113534

Asymmetry parameters for CO 2 around the C K and O K ionization edges from the anisotropy of the ion distributions
journal, June 1995


Photoelectron spectrum and CNDO/2 calculations of HNCO
journal, January 1972

  • Kosmus, W.; Rode, B. M.; Nachbaur, E.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 1, Issue 4
  • DOI: 10.1016/0368-2048(72)80042-2

Autoionization versus photoionization of molecular adsorbates: CO 2 physisorbed on Ni(110)
journal, May 1990


High resolution carbon and oxygen K–LL Auger spectra of carbon dioxide
journal, June 1999

  • Hiltunen, A.; Aksela, S.; Vı́kor, Gy
  • Nuclear Instruments and Methods in Physics Research Section B: Beam Interactions with Materials and Atoms, Vol. 154, Issue 1-4
  • DOI: 10.1016/s0168-583x(99)00049-x

Gaussian basis sets for use in correlated molecular calculations. I. The atoms boron through neon and hydrogen
journal, January 1989

  • Dunning, Thom H.
  • The Journal of Chemical Physics, Vol. 90, Issue 2
  • DOI: 10.1063/1.456153

Rapid reduction of nitrogen oxides in exhaust gas streams
journal, December 1986

  • Perry, R. A.; Siebers, D. L.
  • Nature, Vol. 324, Issue 6098
  • DOI: 10.1038/324657a0

Core-level spectroscopy and dynamics of free molecules
journal, January 2011

  • Feifel, R.; Piancastelli, M. N.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 183, Issue 1-3
  • DOI: 10.1016/j.elspec.2010.04.011

Kinetic modeling of the reduction of nitric oxide in combustion products by isocyanic acid
journal, April 1991

  • Miller, James A.; Bowman, Craig T.
  • International Journal of Chemical Kinetics, Vol. 23, Issue 4
  • DOI: 10.1002/kin.550230403

Imaging the Pair-Correlated HNCO Photodissociation: The NH( a 1 Δ) + CO(X 1 Σ + ) Channel
journal, March 2014

  • Zhang, Zhiguo; Chen, Zhichao; Huang, Cunshun
  • The Journal of Physical Chemistry A, Vol. 118, Issue 13
  • DOI: 10.1021/jp500625m

Observing Femtosecond Fragmentation Using Ultrafast X-ray-Induced Auger Spectra
journal, July 2017

  • Wolf, Thomas; Holzmeier, Fabian; Wagner, Isabella
  • Applied Sciences, Vol. 7, Issue 7
  • DOI: 10.3390/app7070681

Specific production of very long-lived core-excited sulfur atoms by 2p −1 σ* excitation of the OCS molecule followed by ultrafast dissociation
journal, June 2006

  • Fink, Reinhold F.; Eschner, Annika; Magnuson, Martin
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 39, Issue 12
  • DOI: 10.1088/0953-4075/39/12/l03

Single and multiple photoionisation of H2S by 40–250 eV photons
journal, January 2011

  • Eland, J. H. D.; Fink, R. F.; Linusson, P.
  • Physical Chemistry Chemical Physics, Vol. 13, Issue 41
  • DOI: 10.1039/c1cp21654f

Nuclear dynamics of decaying states: A time‐dependent formulation
journal, June 1993

  • Cederbaum, L. S.; Tarantelli, F.
  • The Journal of Chemical Physics, Vol. 98, Issue 12
  • DOI: 10.1063/1.464348

The puzzling behavior of HNCO isomers in molecular clouds
journal, June 2010


Deexcitation electron spectroscopy of core‐excited CO 2 : Comparison of experiment with theory
journal, January 1991

  • Carroll, T. X.; Thomas, T. D.
  • The Journal of Chemical Physics, Vol. 94, Issue 1
  • DOI: 10.1063/1.460386

K-Shell energy loss spectra of 2.5 keV electrons in CO2 and N2O
journal, January 1974


The Auger electron spectrum of water vapour
journal, September 1975


Determination of the K—LL Auger Spectra of N 2 , O 2 , CO, NO, H 2 O, and CO 2
journal, September 1971

  • Moddeman, W. E.; Carlson, Thomas A.; Krause, Manfred O.
  • The Journal of Chemical Physics, Vol. 55, Issue 5
  • DOI: 10.1063/1.1676411

Nuclear dynamics of several decaying overlapping electronic states: A time‐dependent formulation
journal, October 1993

  • Cederbaum, L. S.; Tarantelli, F.
  • The Journal of Chemical Physics, Vol. 99, Issue 8
  • DOI: 10.1063/1.465940

Bond-distance-dependent decay probability of the N 1s →π* core-excited state in N 2
journal, April 2000

  • Piancastelli, M. N.; Fink, R. F.; Feifel, R.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 33, Issue 9
  • DOI: 10.1088/0953-4075/33/9/311

Interatomic resonant Auger effects in core-level photoemission from NO and CS 2 molecules
journal, May 2013

  • Yamazaki, M.; Adachi, J.; Teramoto, T.
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 46, Issue 11
  • DOI: 10.1088/0953-4075/46/11/115101

High-resolution K -shell photoabsorption measurements of simple molecules
journal, August 1991


Theoretical autoionization spectra of excited N2 and N2O
journal, December 1995


A comprehensive study of the vibrationally resolved S 2 p −1 Auger electron spectrum of carbonyl sulfide
journal, July 2012

  • Sekushin, V.; Püttner, R.; Fink, R. F.
  • The Journal of Chemical Physics, Vol. 137, Issue 4
  • DOI: 10.1063/1.4734310

Limitations on the rapid reduction of nitrogen oxides in exhaust gas streams
journal, April 1989

  • Wicke, Brian G.; Grady, Karen A.; Ratcliffe, John W.
  • Nature, Vol. 338, Issue 6215
  • DOI: 10.1038/338492a0

Site-specific formation of metastable dications following inner-shell ionization of CO2
journal, May 2014


K -Shell Auger Transition Rates and Fluorescence Yields for Elements Be-Ar
journal, September 1969


On the interpretation of molecular valence Auger spectra
journal, August 1981

  • Ågren, Hans
  • The Journal of Chemical Physics, Vol. 75, Issue 3
  • DOI: 10.1063/1.442176

Resonant x-ray Raman Scattering involving avoided crossings in the final-state potential-energy curves
journal, November 2000


Dynamics of CO formation in the photodissociation of HNCO and CH2CO at 193nm
journal, March 1982


A new Auger-electron/triple-ion coincidence experiment investigating the decay of deep core excited molecules
journal, January 1996

  • Alkemper, U.; Hörnig, R.; Busch, F. von
  • Journal of Physics B: Atomic, Molecular and Optical Physics, Vol. 29, Issue 1
  • DOI: 10.1088/0953-4075/29/1/009

An experimental and theoretical study of the HNCO+ ion
journal, August 2000


The Photoelectron Spectra of Isocyanic Acid and Related Compounds
journal, November 1970

  • Eland, J. H. D.
  • Philosophical Transactions of the Royal Society A: Mathematical, Physical and Engineering Sciences, Vol. 268, Issue 1184
  • DOI: 10.1098/rsta.1970.0063

Threshold photoelectron spectroscopy of unstable N-containing compounds: Resolution of ΔK subbands in HNCO + and vibrational resolution in NCO +
journal, May 2015

  • Holzmeier, Fabian; Lang, Melanie; Fischer, Ingo
  • The Journal of Chemical Physics, Vol. 142, Issue 18
  • DOI: 10.1063/1.4920951

Vacuum Ultraviolet Photodissociation Dynamics of Isocyanic Acid: The Hydrogen Elimination Channel
journal, October 2013

  • Yu, Shengrui; Su, Shu; Dai, Dongxu
  • The Journal of Physical Chemistry A, Vol. 117, Issue 50
  • DOI: 10.1021/jp407556k

Effects of nuclear dynamics in the low-kinetic-energy Auger spectra of CO and CO2
journal, December 2005

  • Feyer, V.; Bolognesi, P.; Coreno, M.
  • The Journal of Chemical Physics, Vol. 123, Issue 22
  • DOI: 10.1063/1.2137311

Renner−Teller Bending Frequencies of the à 2 Π State of OCS +
journal, May 2007

  • Wheeler, Steven E.; Simmonett, Andrew C.; Schaefer, Henry F.
  • The Journal of Physical Chemistry A, Vol. 111, Issue 20
  • DOI: 10.1021/jp0712046

The resonant Auger spectra of formic acid, acetaldehyde, acetic acid and methyl formate
journal, April 2003


Photodissociation of HNCO at 193 nm. NH(a1Δ) internal energy distribution and reaction rate with O2
journal, July 1979


Role of bending in the dissociation of selective resonant inner-shell excitation as observed in CO 2
journal, March 2000


The vibration-rotation spectrum of HNCO between 1200-450 cm−1
journal, October 1965


K -edge near-edge x-ray-absorption fine structure of oxygen- and carbon-containing molecules in the gas phase
journal, July 1989


Photoelectron spectra of some group 4 pseudohalides and related compounds
journal, January 1972

  • Cradock, S.; Ebsworth, E. A. V.; Murdoch, J. D.
  • Journal of the Chemical Society, Faraday Transactions 2, Vol. 68
  • DOI: 10.1039/f29726800086

Surprising similarities in the spectator decay of oxygen core‐excited CO, CO 2 , and OCS
journal, April 1989

  • Carroll, T. X.; Thomas, T. D.
  • The Journal of Chemical Physics, Vol. 90, Issue 7
  • DOI: 10.1063/1.455857

The resonant Auger electron spectrum of C 1s−1π* excited ethene: A combined theoretical and experimental investigation
journal, April 2000

  • Fink, Reinhold F.; Sorensen, Stacey L.; de Brito, Arnaldo Naves
  • The Journal of Chemical Physics, Vol. 112, Issue 15
  • DOI: 10.1063/1.481241

Infra-red spectrum and structure of the HNCO molecule
journal, January 1950


High-resolution inner-shell spectroscopies of free atoms and molecules using soft-x-ray beamlines at the third-generation synchrotron radiation sources
journal, February 2003


Infrared spectrum of isocyanic acid between 465 and 1100 cm−1
journal, June 1979


Resonant Auger decay study of core-excited OCS
journal, August 2009

  • Travnikova, O.; Miron, C.; Bässler, M.
  • Journal of Electron Spectroscopy and Related Phenomena, Vol. 174, Issue 1-3
  • DOI: 10.1016/j.elspec.2009.08.003

High-resolution study of resonant decay following the O 1s → π∗ excitation(s) in CO2: evidence for an overlapping Rydberg transition
journal, August 1997


SCF and limited CI calculations for assignment of the Auger spectrum and of the satellites in the soft X-ray spectrum of H2O
journal, September 1975