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The electronic spectrum of s-tetrazine: Structures and vibrational frequencies of the ground and excited electronic states
The ground and excited electronic states of the s-tetrazine molecule have been studied using the methods of ab initio electronic structure theory. In particular, complete self-consistent field (SCF) o...
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Exact analytic formula for calculating Franck–Condon factors using the Kratzer potential
To calculate Franck–Condon factors (i.e., squares of the vibrational overlap integrals for two electronic states of a diatomic molecule), the potential energy curve in each state is approximated...

Vertical and adiabatic ionization energies of NH<sup> - </sup><sub>4</sub> isomers via electron propagator theory and many body perturbation theory calculations with large basis sets

J. Chem. Phys. 87, 3557 (1987); doi:10.1063/1.453000

Issue Date: 15 September 1987

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J. V. Ortiz
Department of Chemistry, University of New Mexico, Albuquerque, New Mexico 87131
Electron propagator theory (EPT) is applied to calculating vertical ionization energies of NH<sup> - </sup><sub>4</sub> in two stable geometries. The first is a complex of a hydride coordinated to one of the hydrogens of the solvent ammonia molecule, while the other isomer has tetrahedral symmetry. Both structures have been optimized using second order many body perturbation theory with a 6-311++G(d) basis. The former structure is predicted to be 0.42 eV more stable than the latter. A series of third order EPT quasiparticle calculations is carried out to demonstrate basis set saturation. The best EPT calculations give vertical ionization energies of 1.20 eV for the solvated hydride structure and 0.42 eV for the tetrahedral isomer. Both of these calculations are within 0.1 eV of anion photoelectron spectroscopy peaks and suggest that the tetrahedral isomer is responsible for one of these features. After removing an electron from the solvate structure, the complex settles into a shallow van der Waals minimum with a hydrogen atom weakly bound to the ammonia molecule. Calculations on the tetrahedral neutral indicate that there is little relaxation energy along the neutral final state potential energy surface, explaining the sharpness of the observed photoelectron peak. The Journal of Chemical Physics is copyrighted by The American Institute of Physics.
History: Received 16 April 1987; accepted 4 June 1987
Permalink: http://link.aip.org/link/?JCPSA6/87/3557/1
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KEYWORDS and PACS

Keywords
PACS
  • 31.20.Tz
    Electronic structure of atoms and molecules: theory Specific calculations and results Electron correlation and CI calculations
  • 35.20.Vf
    Experimentally derived information on atoms and molecules; instrumentation and techniques Molecules Ionization potentials, electron affinities, molecular core binding energy
  • 33.60.Cv
    Molecular spectra and interactions of molecules with photons Photoelectron spectra Ultraviolet and vacuum ultraviolet photoelectron spectra
  • YEAR: 1987

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ISSN:
0021-9606 (print)   1089-7690 (online)
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REFERENCES (16)
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