Theoretical Transition Probabilities
- 1 March 1966
- journal article
- Published by AIP Publishing in The Journal of Chemical Physics
- Vol. 44 (5), 1888-1898
- https://doi.org/10.1063/1.1726958
Abstract
The contribution to the intensity of atomic and molecular electronic transitions beyond the Hartree—Fock, or independent-particle model, is examined by means of ``many-electron theory'' (MET). The contribution is of first order in the wavefunctions of the combining states. MET analysis of the off-diagonal matrix element for the transition probability in the frozen-core approximation yields physically interesting expressions which are applied to atomic and molecular examples. Considerable improvement in calculated atomic (e.g., Be resonance transition) and molecular (e.g., π—π* transitions) intensities are obtained when analysis shows that ground-state ``hole pairs'' are strongly scattered into the orbital sea of the excited state. The uses of energies and operators in the calculation of electronic intensities is also examined. The relation between the expectation values of operators ∇ and r which replaces the widely used off-diagonal hypervirial theorem in the absence of exact wavefunctions is given.Keywords
This publication has 20 references indexed in Scilit:
- Quantum Theory of Atoms and MoleculesAnnual Review of Physical Chemistry, 1964
- Values for Transitions between the,, and, and the,,, andStates in HeliumPhysical Review B, 1964
- Recent Developments in Perturbation TheoryPublished by Elsevier ,1964
- Many‐Electron Theory of Atoms, Molecules and Their InteractionsAdvances in Chemical Physics, 1964
- Constrained Molecular Wavefunctions: HF MoleculeThe Journal of Chemical Physics, 1963
- Variation-Perturbation Method for Excited StatesPhysical Review B, 1961
- The Electronic Spectra of Cata-Condensed HydrocarbonsThe Journal of Chemical Physics, 1954
- Transition Probabilities. II. Calculation of Semi-Theoretical f-Numbers for Hydrogen Using the Dipole Velocity OperatorThe Journal of Chemical Physics, 1952
- The Continuous Absorption Coefficient of the Helium Atom.The Astrophysical Journal, 1948
- On the Continuous Absorption Coefficient of the Negative Hydrogen IonThe Astrophysical Journal, 1945