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Double Rydberg anions: Photoelectron spectroscopy of NH<sub>4</sub><sup>-</sup>, N2H<sub>7</sub><sup>-</sup>, N3H<sub>10</sub><sup>-</sup>, N4H<sub>13</sub><sup>-</sup>, and N5H<sub>16</sub><sup>-</sup>
We report the discovery and photoelectron spectroscopic study of the four double Rydberg anions: N2H7-" align="middle"/>, N3H10-" align="middle"/>, N4H13-" align="middle"/>, and N5H16-" align="middle"...
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First principles determination of the photoelectron spectrum of LiH–
The photoelectron spectra of LiH– and LiD– have been determined from a first principles theoretical treatment using techniques which very accurately reproduce the experimentally known electr...

A double Rydberg anion with a hydrogen bond and a solvated double Rydberg anion: Interpretation of the photoelectron spectrum of N2H<sub>7</sub><sup>-</sup>

J. Chem. Phys. 117, 5748 (2002); doi:10.1063/1.1499492

Issue Date: 22 September 2002

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J. V. Ortiz
Department of Chemistry, Kansas State University, Manhattan, Kansas 66506-3701
A double Rydberg anion has two electrons in diffuse orbitals that are bound by a closed-shell, cationic core. Low-energy features in the recently reported photoelectron spectrum of N2H<sub>7</sub><sup>-</sup> are assigned to double Rydberg anions on the basis of electron propagator calculations employing Brueckner doubles, coupled-cluster reference states. The lowest electron detachment energy, 0.415 eV, corresponds to an initial state consisting of a hydrogen-bridged N2H<sub>7</sub><sup>+</sup> core and two diffuse electrons. A feature at slightly higher energy, 0.578 eV, belongs to a complex that comprises a tetrahedral NH<sub>4</sub><sup>-</sup> double Rydberg anion and an ammonia solvent molecule. The most intense peak in the photoelectron spectrum, which occurs at 1.460 eV, pertains to a complex with a hydride anion and two ammonia solvent molecules. Plots of Dyson orbitals associated with electron detachment energies facilitate qualitative interpretation of electronic structure in the anions and in the neutral final states. Vibrational structure associated with each of these features has been interpreted as well. Previous assignments of electron detachment energies to the hydride–ammonia and tetrahedral isomers of NH<sub>4</sub><sup>-</sup> have been confirmed with the present methods. Vibrationally excited final states have been assigned for this spectrum also.©2002 American Institute of Physics.
History: Received 23 May 2002; accepted 19 June 2002
Permalink: http://link.aip.org/link/?JCPSA6/117/5748/1
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EDITORIALLY RELATED

  1. Double Rydberg anions: Photoelectron spectroscopy of NH<sub>4</sub><sup>-</sup>, N2H<sub>7</sub><sup>-</sup>, N3H<sub>10</sub><sup>-</sup>, N4H<sub>13</sub><sup>-</sup>, and N5H<sub>16</sub><sup>-</sup>
    S.-J. Xu et al.
    J. Chem. Phys. 117, 5742 (2002)

KEYWORDS and PACS

Keywords
PACS
  • 33.60.-q
    Molecular properties and interactions with photons Photoelectron spectra
  • 33.15.Fm
    Molecular properties and interactions with photons Properties of molecules Bond strengths, dissociation energies
  • 31.15.Dv
    Electronic structure of atoms and molecules: theory Calculations and mathematical techniques in atomic and molecular physics (excluding electron correlation calculations) Coupled-cluster theory
  • YEAR: 2002

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