Many-body theory of the ionization energies of CH/sub 3//sup -/, SiH/sub 3//sup -/, and GeH/sub 3//sup -/

Journal Article · Wed Aug 19 00:00:00 EDT 1987 · J. Am. Chem. Soc.; (United States)

DOI:https://doi.org/10.1021/ja00251a003· OSTI ID:6087074

Ortiz, J V

Electron propagator theory is used to calculate the vertical ionization energies of CH/sub 3//sup -/, SiH/sub 3//sup -/, and GeH/sub 3//sup -/. Basis set augmentations are made until changes in the computational results are small. Adiabatic ionization energies are obtained via many-body-perturbation-theory calculations on the neutral potential energy surface. The adiabatic values are in excellent agreement with photoelectron spectroscopy measurements on CH/sub 3//sup -/ and SiH/sub 3//sup -/. Comparable calculations are made for GeH/sub 3//sup -/. Calculated vertical ionization energies are 0.51 eV for CH/sub 3//sup -/, 1.79 eV for SiH/sub 3//sup -/, and 2.01 eV for GeH/sub 3//sup -/; adiabatic counterparts are 0.19, 1.31, and 1.39 eV, respectively. Calculations employing effective core potentials for SiH/sub 3//sup -/ and GeH/sub 3//sup -/ agree closely with all-electron results. Vertical ionization energies employing these techniques are 1.88 eV for SiH/sub 3//sup -/ and 1.97 eV for GeH/sub 3//sup -/. Adiabatic effective core potential results are 1.46 eV for SiH/sub 3//sup -/ and 1.49 eV for GeH/sub 3//sup -/.

• Research Organization: Univ. of New Mexico, Albuquerque
• OSTI ID: 6087074
• Journal Information: J. Am. Chem. Soc.; (United States), Journal Name: J. Am. Chem. Soc.; (United States) Vol. 109:17; ISSN JACSA
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
400201* -- Chemical & Physicochemical Properties
ALKYL RADICALS
ANIONS
CHARGED PARTICLES
DATA
GERMANIUM COMPOUNDS
HYDROGEN COMPOUNDS
INFORMATION
IONIZATION POTENTIAL
IONS
MATHEMATICAL MODELS
METHYL RADICALS
MOLECULAR MODELS
NUMERICAL DATA
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SILICON COMPOUNDS
THEORETICAL DATA