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An annealing schedule, T(t), is the temperature as function of time whose goal is to bring a system from some initial low-order state to a final high-order state. We use the probability in the lowest ...
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Evidence of Fermi resonance in core-ionized methane
A full quartic potential energy surface is determined for core-ionized methane and used to investigate coupling between vibrational modes. A strong Fermi resonance is found between the first excited s...

Accurate and approximate calculations of Franck–Condon intensities in the carbon 1s photoelectron spectrum of methane

J. Chem. Phys. 112, 7979 (2000); doi:10.1063/1.481398

Issue Date: 8 May 2000

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Tor Karlsen and Knut J. Børve
Department of Chemistry, University of Bergen, Allégaten 41, N-5007 Bergen, Norway
The level of theory needed in order to accurately compute the bond contraction following core ionization in methane is examined with an emphasis on one-electron bases and treatment of electron correlation. At our highest level of theory, including core–valence electron correlation, a value of 4.82 pm is computed for the bond contraction in core-ionized methane, in good agreement with experimental findings. The associated potential energy curve in the symmetric stretching coordinate is used to form relative intensities of the peaks in the C  1s photoelectron spectrum of methane. For use in more approximate studies, it is proposed that the ionized core may be conveniently represented by effective core potentials during geometry optimization, and the prospect of this approach is explored in some depth. ©2000 American Institute of Physics.
History: Received 2 November 1999; accepted 15 February 2000
Permalink: http://link.aip.org/link/?JCPSA6/112/7979/1
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EDITORIALLY RELATED

  1. Evidence of Fermi resonance in core-ionized methane
    Tor Karlsen et al.
    J. Chem. Phys. 112, 7986 (2000)

KEYWORDS and PACS

Keywords
PACS
  • 33.60.-q
    Molecular properties and interactions with photons Photoelectron spectra
  • 33.70.Ca
    Molecular properties and interactions with photons Intensities and shapes of molecular spectral lines and bands Oscillator and band strengths, lifetimes, transition moments, and Franck–Condon factors
  • 33.70.Fd
    Molecular properties and interactions with photons Intensities and shapes of molecular spectral lines and bands Absolute and relative line and band intensities
  • 31.25.Qm
    Electronic structure of atoms, molecules and their ions: theory Electron correlation calculations for atoms and molecules Electron correlation calculations for polyatomic molecules
  • YEAR: 2000

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PUBLICATION DATA

ISSN:
0021-9606 (print)   1089-7690 (online)
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