Calculation of Spin-Orbit Coupling Constants in Diatomic Molecules from Hartree-Fock Wave Functions

1969 ◽  
Vol 177 (1) ◽  
pp. 100-101 ◽  
Author(s):  
T. E. H. Walker ◽  
W. G. Richards
Keyword(s):  
Diatomic Molecules ◽  
Wave Functions ◽  
Coupling Constants ◽  
Orbit Coupling ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Hartree Fock

Theory of spin-orbit coupling in atoms, II. Comparison of theory with experiment

1963 ◽  
Vol 271 (1347) ◽  
pp. 565-578 ◽  
Keyword(s):  
Wave Functions ◽  
Coupling Constants ◽  
Orbit Coupling ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Outer Electron ◽  
Coupling Constant ◽  
Radial Wave ◽  
Order Of Magnitude ◽  
Experimental Values

Results of calculations of the spin-orbit coupling constant for 2 p , 3 p , 4 p , and 3 d shell ions and atoms are presented. The calculations are based on a theory developed in a previous paper. Excellent agreement of this theory with experiment is obtained for the 2 p and 3 d shell ions, while calculations using the familiar < ∂ V / r ∂ r > expression for the coupling constant lie 10 to 20 % too high. The exchange terms discussed in the earlier paper make a contribution to the coupling constant of the same sign and order of magnitude as the ordinary shielding terms. For the 3 p and 4 p shell atoms, the calculated coupling constants based on the exact theory and on the < ∂ V / r ∂ r > expression both tend to lie below the experimental values. An explanation for this disagreement is suggested, based on the noded nature of the outer-electron radial wave functions for these atoms. The importance of the residual-spin-other-orbit interaction is discussed, and it is shown that ignoring the form of this interaction may lead to a large variation in the coupling constant within a configuration.

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