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Title: Single photon simultaneous K-shell ionization and K-shell excitation. II. Specificities of hollow nitrogen molecular ions

Abstract

The formalism developed in the companion Paper I is used here for the interpretation of spectra obtained recently on the nitrogen molecule. Double core-hole ionization K{sup −2} and core ionization-core excitation K{sup −2}V processes have been observed by coincidence electron spectroscopy after ionization by synchrotron radiation at different photon energies. Theoretical and experimental cross sections reported on an absolute scale are in satisfactory agreement. The evolution with photon energy of the relative contribution of shake-up and conjugate shake-up processes is discussed. The first main resonance in the K{sup −2}V spectrum is assigned to a K{sup −2}π{sup ∗} state mainly populated by the 1s→ lowest unoccupied molecular orbital dipolar excitation, as it is in the K{sup −1}V NEXAFS (Near-Edge X-ray Absorption Fine Structure) signals. Closer to the K{sup −2} threshold Rydberg resonances have been also identified, and among them a K{sup −2}σ{sup ∗} resonance characterized by a large amount of 2s/2p hybridization, and double K{sup −2}(2σ{sup ∗}/1π/3σ){sup −1}1π{sup ∗2} shake-up states. These resonances correspond in NEXAFS spectra to, respectively, the well-known σ{sup ∗} shape resonance and double excitation K{sup −1}(2σ{sup ∗}/1π/3σ){sup −1}1π{sup ∗2} resonances, all being positioned above the threshold.

Authors:
; ; ; ; ;  [1];  [2]; ;  [3];  [4];  [5];  [6];  [7]
  1. Laboratoire de Chimie Physique-Matière et Rayonnement, UMR 7614, Sorbonne Universités, UPMC University of Paris 6, 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05 (France)
  2. (UMR 7614), CNRS, 11 rue Pierre et Marie Curie, 75231 Paris Cedex 05 (France)
  3. Jozef Stefan Institute, P.O. Box 3000, SI-1001 Ljubljana (Slovenia)
  4. Department of Chemistry, Tokyo Institute of Technology, Meguro-ku, Tokyo 152-8551 (Japan)
  5. (Japan)
  6. Department of Environmental Science, Niigata University, Niigata 950-2181 (Japan)
  7. Photon Factory, Institute of Materials Structure Science, Tsukuba, Ibaraki 305-0801 (Japan)
Publication Date:
OSTI Identifier:
22415460
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 1; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; ABSORPTION SPECTROSCOPY; CROSS SECTIONS; ELECTRON SPECTROSCOPY; EXCITATION; FINE STRUCTURE; IONIZATION; K SHELL; MOLECULAR IONS; MOLECULAR ORBITAL METHOD; MOLECULES; NITROGEN; PHOTONS; RESONANCE; SYNCHROTRON RADIATION; X-RAY SPECTROSCOPY

Citation Formats

Carniato, S., E-mail: stephane.carniato@upmc.fr, Selles, P., Andric, L., Palaudoux, J., Penent, F., Lablanquie, P., LCPMR, Žitnik, M., Bučar, K., Nakano, M., Photon Factory, Institute of Materials Structure Science, Tsukuba, Ibaraki 305-0801, Hikosaka, Y., and Ito, K. Single photon simultaneous K-shell ionization and K-shell excitation. II. Specificities of hollow nitrogen molecular ions. United States: N. p., 2015. Web. doi:10.1063/1.4904274.
Carniato, S., E-mail: stephane.carniato@upmc.fr, Selles, P., Andric, L., Palaudoux, J., Penent, F., Lablanquie, P., LCPMR, Žitnik, M., Bučar, K., Nakano, M., Photon Factory, Institute of Materials Structure Science, Tsukuba, Ibaraki 305-0801, Hikosaka, Y., & Ito, K. Single photon simultaneous K-shell ionization and K-shell excitation. II. Specificities of hollow nitrogen molecular ions. United States. doi:10.1063/1.4904274.
Carniato, S., E-mail: stephane.carniato@upmc.fr, Selles, P., Andric, L., Palaudoux, J., Penent, F., Lablanquie, P., LCPMR, Žitnik, M., Bučar, K., Nakano, M., Photon Factory, Institute of Materials Structure Science, Tsukuba, Ibaraki 305-0801, Hikosaka, Y., and Ito, K. 2015. "Single photon simultaneous K-shell ionization and K-shell excitation. II. Specificities of hollow nitrogen molecular ions". United States. doi:10.1063/1.4904274.
@article{osti_22415460,
title = {Single photon simultaneous K-shell ionization and K-shell excitation. II. Specificities of hollow nitrogen molecular ions},
author = {Carniato, S., E-mail: stephane.carniato@upmc.fr and Selles, P. and Andric, L. and Palaudoux, J. and Penent, F. and Lablanquie, P. and LCPMR and Žitnik, M. and Bučar, K. and Nakano, M. and Photon Factory, Institute of Materials Structure Science, Tsukuba, Ibaraki 305-0801 and Hikosaka, Y. and Ito, K.},
abstractNote = {The formalism developed in the companion Paper I is used here for the interpretation of spectra obtained recently on the nitrogen molecule. Double core-hole ionization K{sup −2} and core ionization-core excitation K{sup −2}V processes have been observed by coincidence electron spectroscopy after ionization by synchrotron radiation at different photon energies. Theoretical and experimental cross sections reported on an absolute scale are in satisfactory agreement. The evolution with photon energy of the relative contribution of shake-up and conjugate shake-up processes is discussed. The first main resonance in the K{sup −2}V spectrum is assigned to a K{sup −2}π{sup ∗} state mainly populated by the 1s→ lowest unoccupied molecular orbital dipolar excitation, as it is in the K{sup −1}V NEXAFS (Near-Edge X-ray Absorption Fine Structure) signals. Closer to the K{sup −2} threshold Rydberg resonances have been also identified, and among them a K{sup −2}σ{sup ∗} resonance characterized by a large amount of 2s/2p hybridization, and double K{sup −2}(2σ{sup ∗}/1π/3σ){sup −1}1π{sup ∗2} shake-up states. These resonances correspond in NEXAFS spectra to, respectively, the well-known σ{sup ∗} shape resonance and double excitation K{sup −1}(2σ{sup ∗}/1π/3σ){sup −1}1π{sup ∗2} resonances, all being positioned above the threshold.},
doi = {10.1063/1.4904274},
journal = {Journal of Chemical Physics},
number = 1,
volume = 142,
place = {United States},
year = 2015,
month = 1
}
  • We present in detail a theoretical model that provides absolute cross sections for simultaneous core-ionization core-excitation (K{sup −2}V ) and compare its predictions with experimental results obtained on the water molecule after photoionization by synchrotron radiation. Two resonances of different symmetries are assigned in the main K{sup −2}V peak and comparable contributions from monopolar (direct shake-up) and dipolar (conjugate shake-up) core-valence excitations are identified. The main peak is observed with a much greater width than the total experimental resolution. This broadening is the signature of nuclear dynamics.
  • We investigate simultaneous excitation and fluorescence detection of OH and H in flames, using frequency-doubled (308-nm) and frequency-tripled (205-nm) beams generated using a single dye-laser system. {copyright} 1990 Optical Society of America
  • The formation of hollow molecules (with a completely empty K shell in one constituent atom) through single-photon core double ionization has been demonstrated using a sensitive magnetic bottle experimental technique combined with synchrotron radiation. Detailed properties are presented such as the spectroscopy, formation, and decay dynamics of the N{sub 2}{sup 2+} K{sup -2} main and satellite states and the strong chemical shifts of double K holes on an oxygen atom in CO, CO{sub 2}, and O{sub 2} molecules.
  • Absolute optical emission cross sections have been measured for transitions of the N/sup +/ ion in the wavelength range 3800--7000 A originating from 33 terms of the N/sup +/(2s/sup 2/2pnl) or N/sup +/(2s2p/sup 2/nl) configurations with n from 3 to 6 produced by electron-impact ionization and dissociation of the N/sub 2/ molecule. The incident electron energy ranges from threshold to 450 eV. The excitation functions show a broad maximum at about 190 eV. The mechanisms of formation of the excited atomic nitrogen ions near the threshold energy are discussed.
  • Ion specificity, a widely observed macroscopic phenomenon in condensed phases and at interfaces, is essentially a fundamental chemical physical issue. We have been investigating such effects using cluster models in an “atom-by-atom” and “molecule-by-molecule” fashion not possible with condensed-phase methods. We use electrospray ionization (ESI) to generate molecular and ionic clusters to simulate key molecular entities involved in local binding regions, and characterize them employing negative ion photoelectron spectroscopy (NIPES). Inter- and intramolecular interactions and binding configurations are directly obtained as functions of cluster size and composition, providing insightful molecular-level description and characterization over the local active sites that playmore » crucial roles in determining solution chemistry and condensed phase phenomena. Finally, the topics covered in this article are relevant to a wide scope of research fields ranging from ion specific effects in electrolyte solutions, ion selectivity/recognition in normal functioning of life, to molecular specificity in aerosol particle formation, as well as in rational material design and synthesis.« less
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