The effective rotational hamiltonian for open-shell molecules

1 January 1969

journal article
research article
Published by Taylor & Francis in Molecular Physics

Vol. 16 (2) , 105-120
https://doi.org/10.1080/00268976.1969.10310422

Abstract

A formalism for obtaining the effective rotational hamiltonian for any open-shell molecule is described. This effective hamiltonian is shown to be formed of series of irreducible tensors composed of real and fictitious angular momentum operators. The operations of these tensors may in all cases be restricted to a particular electronic state. Application of such a formalism should be particularly valuable in the interpretation of the high resolution spectra (zero-field microwave, gas-phase electron resonance, etc.) of open-shell molecules, for it follows that the experimental data may always be interpreted without explicit reference to electronic states other than that wherein the spectrum originates. Useful rules are given which determine the relevant orders of tensors in the series and the method is illustrated for the case of a ³Σ diatomic molecule.

Keywords

This publication has 15 references indexed in Scilit:

Electron resonance of SO ( ³ Ʃ ) in the gas phase
Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1967
$L$ -Uncoupling Effects on the Electron-Paramagnetic-Resonance Spectra of $N^{14}$ $O^{16}$ and $N^{15}$ $O^{16}$
Physical Review B, 1966
Electron resonance of electronically excited SO( ¹ ∆) in the gas phase
Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1966
Electron Resonance Studies of Free Radicals in the Gas Phase. Detection of ClO, BrO, and NS
The Journal of Chemical Physics, 1966
Similarity between the Spin-Spin and Spin-Orbit Interactions in the Diatomic Molecules
Physical Review B, 1962
ON THE SPIN–ORBIT INTERACTION IN DIATOMIC MOLECULES. I
Canadian Journal of Physics, 1958
Theory of the Fine Structure of the Molecular Oxygen Ground State
Physical Review B, 1955
The Coupling of Angular Momentum Vectors in Molecules
Reviews of Modern Physics, 1951
Theory of the nuclear hyperfine structure of paramagnetic resonance spectra in crystals
Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 1951
A Modified Perturbation Procedure for a Problem in Paramagnetism
Proceedings of the Physical Society. Section A, 1950