Ground and excited state adiabatic 2A″ and 2A′ potential energy surfaces of the (Kr–O2)+ cluster ion

Ramiro Díaz, B. and Wahnón Benarroch, Perla (1996). Ground and excited state adiabatic 2A″ and 2A′ potential energy surfaces of the (Kr–O2)+ cluster ion. "Journal of Chemical Physics", v. 104 (n. 1); pp. 191-199. ISSN 0021-9606. https://doi.org/10.1063/1.470888.

Description

Title: Ground and excited state adiabatic 2A″ and 2A′ potential energy surfaces of the (Kr–O2)+ cluster ion
Author/s:
  • Ramiro Díaz, B.
  • Wahnón Benarroch, Perla
Item Type: Article
Título de Revista/Publicación: Journal of Chemical Physics
Date: 1996
ISSN: 0021-9606
Volume: 104
Subjects:
Freetext Keywords: Adiabatic potential energy surfaces
Faculty: E.T.S.I. Telecomunicación (UPM)
Department: Tecnologías Especiales Aplicadas a la Telecomunicación [hasta 2014]
Creative Commons Licenses: Recognition - No derivative works - Non commercial

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Abstract

The seven lowest adiabatic potential energy surfaces (PES) of the (Kr–O2)+ cluster ion in each of the 2A″ and 2A′ symmetries are calculated. The computational method involves configuration interaction calculations in a basis of a thousand projected valence‐bond state functions. It resorts to diagonal corrections of the Hamiltonian matrix prior to configuration interaction and makes use of an l‐dependent pseudopotential for Kr. The results are characterized by the shallowness of the 1 2A″ potential well and the absence of wells in the other PES investigated. The 1 2A″ equilibrium characteristics differ significantly from those proposed in other work. Notable effects on all the PES are observed when the O–O bond is stretched beyond 2.5a0. No 1 2A′−2 2A′ (nor 1 2A″−2 2A″) pseudocrossings are found that could explain, on the basis of mere electronic structure arguments, the available thermal energy charge transfer data. A 2 2A″−1 2A′ crossing actually exists but the related Coriolis coupling mechanism cannot be invoked for low energy <1 eV encounters. This draws attention to alternative more subtle dynamic charge transfer mechanisms possibly involving quartet‐doublet spin–orbit transitions and/or (near) degeneracies of rovibronic, instead of mere electronic, energy levels. Evidence is shown for pseudocrossing mechanisms of population sharing between the 2,3A″ and 2A′ states. Similar evidence is shown for an O2(X 3Σ−g)→O2(a 1Δg) excitation involving two electron rearrangement.

Funding Projects

TypeCodeAcronymLeaderTitle
Government of SpainPB92-1082UnspecifiedUnspecifiedUnspecified
UnspecifiedCHRX-CT93-0150UnspecifiedUnspecifiedUnspecified

More information

Item ID: 62643
DC Identifier: http://oa.upm.es/62643/
OAI Identifier: oai:oa.upm.es:62643
DOI: 10.1063/1.470888
Deposited by: Biblioteca ETSI Telecomunicación
Deposited on: 29 May 2020 12:30
Last Modified: 29 May 2020 12:30
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