Abstract
For chemical purposes the electronic structure of molecules composed of light elements is well described by the Schrödinger equation employing a non-relativistic, spin-independent Hamiltonian. Spin degrees of freedom enter the scene only because electrons ― being fermions ― obey the Pauli principle, i.e., the total electronic wavefunction has to be antisymmetric with respect to the interchange of two electronic coordinates. At this level of approximation no mixing of spin and spatial symmetries occurs. Eigenfunctions of the electronic Schrodinger equation can simultaneously be made eigenfunctions of the total spin \({\vec S^2}\) with eigenvalues s(s + 1). Their spatial parts show characteristic transformation properties under symmetry operations, e.g. rotations and reflections of the nuclear frame. Therefore, we use to classify electronic states according to their spin multiplicity 2s + 1 and according to some irreducible representation of the molecular point group.
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Marian, C.M. (1997). Fine and Hyperfine Structure. In: Wilson, S., Diercksen, G.H.F. (eds) Problem Solving in Computational Molecular Science. NATO ASI Series, vol 500. Springer, Dordrecht. https://doi.org/10.1007/978-94-009-0039-4_9
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DOI: https://doi.org/10.1007/978-94-009-0039-4_9
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