Operator orbital paramagnetic

En. The orbital paramagnetic operator, on the other hand, is spin free and the summation is therefore over states of the same spin symmetry as... 

The equivalent of the spin-other-orbit operator in eq. (8.30) splits into two contributions, one involving the interaction of the electron spin with the magnetic field generated by the movement of the nuclei, and one describing the interaction of the nuclear spin with the magnetic field generated by the movement of the electrons. Only the latter survives in the Born-Oppenheimer approximation, and is normally called the Paramagnetic Spin-Orbit (PSO) operator. The operator is the one-electron part of... 

The expression for the contribution to the spin-orbit induced MCD intensity from perturbation of the ground state is somewhat reminiscent of an expression for the Ag quantity of EPR spectroscopy. The similarity lies in the paramagnetic term, Agp. This term is composed of integrals of a spin-orbit operator over molecular orbitals similar to the expression for the perturbation of the ground state in the presence of spin-orbit coupling (Eqs. 52-56). The paramagnetic contribution to Ag dominates for blue copper proteins and it was suspected that the MCD parameters and Amay have some sort of relationship. It was found that many of the terms that make large contributions to AgP do play a role in the MCD intensity but no simple relationship was found (160). 

From the three operators obtained by differentiating the Hamiltonian with respect to the nuclear magnetic moments (Equation (2.12)) only the singlet paramagnetic spin-orbital (PSO) operator... 

The q = 1 components of T (L) will be neglected because they involve the mixing of excited states with the ground vibronic state, giving rise to temperature-independent paramagnetism. With this simplification the matrix elements of the orbital Zeeman interaction operating within the ground vibronic state are... 

While the chemical interpretation of the e parameters is a matter of real concern to us, there are also several other difficulties which are, however, more apparent than real. Consider the question of the calculation of magnetic properties in transition metal complexes - paramagnetic susceptibilities and e.s.r. g values. In contrast to the study of eigenvalues for optical transition energies, these require descriptions of the wavefunc-tions after the perturbation by the ligand field, interelectron repulsion and spin-orbit coupling effects. In susceptibility calculations it is customary to use Stevens orbital reduction factor k in the magnetic moment operator... 

Paramagnetic Spin-Orbit (PSO) operator. The operator is the one-electron part of which in its time-independent form (setting A = 0 in eq. (8.81) can be written as ... 

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