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Extra resources for Advanced Inorganic Chemistry: a Comprehensive Text, 3rd Edition,
Ref. 17. 429 4799,9 0,269 0,075 -0,0081 (J,(JOO13 0,0068 55,29 0,832 0,506 -0,052 -(J,0013 0,355 ,,-+00 '" and 11 = 6. 8. 10, The /s are dimensionless quantities called anistropy factors and the values of the most important ones are given in Table 8. 62) and those defined in eqs. 63) 12£222 From Table 8 it is seen that the isotropic dispersion coefficients en calculated by Mulder et al. 1. 65) where the coefficients are given in Table 9. The coefficients e l 6 are about 50~o larger than those in eq.
16. H. Bredohl and G. Herzberg, The Lyman and Werner bands of deuterium, Can. J. Phys. 51,867-887 (1973). 17. J. Dabrowski and G. Herzberg, The absorption and emission spectra of HD in the vacuum ultraviolet, Can. J. Phys. 54, 525-567 (1967). 18. P. R. Bunker, On the breakdown of the Born-Oppenheimer approximation for diatomic molecules. J. Mol. Spectrosc. 42, 478-494 (1972). 19. P. A. M. Dirac, The Principles of Quantum Mechanics, Oxford University Press, New York (1958). 20. R. K. Pathria, Statistical Mechanics, Pergamon Press, New York (1972).
The quantity of central interest is the expectation value of the total energy of the system over the properly antisymmetrized electronic ground state of the interacting molecules. The non adiabatic effects arising from the mixing of the different electronic states as a result of the nuclear motion can be expected to be small, since these effects are small in the isolated molecules. The intermolecular interaction may therefore be defined in terms of the total energy of the system in the lowest electronic state for clamped nuclei, usually called the Born-Oppenheimer approximation.