Calculation of the vertical electron attachment energy of carbon dioxide: Continuum states for negative ions

✍ Scribed by Pablo J. Bruna; Sigrid D. Peyerimhoff; Robert J. Buenker

• Publisher: Elsevier Science
• Year: 1976
• Tongue: English
• Weight: 685 KB
• Volume: 39
• Category: Article
• ISSN: 0009-2614
• DOI: 10.1016/0009-2614(76)80057-7

✦ Synopsis

Ab initio SCF and CI calculations employing a relatively large basis set including various polarization and diffuse (Rydberg-type) functions find the lowest-lying valence-shell state of CO? to be 5.14 eV less stable than carbon dioxide itself in the linear equilibrium geometry of the latter. Many lower-energy states of the neative ion with diffuse outer-electron charge distributions are indicated, however, and it is concluded that the spectrum of fineur CO; consists of a continuum joining onto the CO2 ground state level in the limit of complete electron detachment. Since the energy of the valence-shell CO;

(resonance) state is apparently much too hish to explain the rate constant studies for vertical electron attachment to carbon dioxide, it is suggested that one or more of the less diffuse of these Rydberg-like continuum species of the negative ion may in fact participate in this reaction. * Senior U.S. Scientist Awardee of the Alexander von Humboldt Foundation.