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Extra resources for Advances in Chemical Physics: Intermolecular Forces, Volume 12
In order to have a dipole moment, an atom must be hybridized with a wave function which is a mixture of quantum states of different panties (as illustrated in Fig. 2). Except for the hydrogen atom (where, for example, the 2s and 2p states have different parity), atomic states having the same energy have the same parity. Thus, insofar as nonresonant atomic collisions are concerned, the dipoledipole interactions can be ignored. However, atoms which are not in an S state can have a quadrupole moment.
Ken5c remarks that it is extremely easy to make mistakes in the sign of w. One can classify resonances according to the order of perturbation and the type of perturbation which destroys the resonant degeneracy. Thus, we start by considering first-order dipole resonance which concerns interactions where the degeneracy is destroyed by the firstorder perturbation with respect to the electric dipole-electric dipole interaction potential, V,. # 0 then the lead term in b. First-Order Dipole Resonance.
For our purposes, however, it is more useful t o write the V,, in the more familiar Cartesian component representation. For example, for the interaction of neutral atoms, V , = V , = 0. Thus V 3 R - 3 ,the lead term in the multipole expansion of the interaction potential for neutral atoms, can be written in either of the forms = p a ' pb - 3(pa * a)(pb ' 8 ) (51) where fl is the unit vector in the direction of the polar axis and p,, = rai and pb = rbj are, respectively, the instantaneous electro- -c i -1 j static dipole moments of the atoms a and b.
Advances in Chemical Physics: Intermolecular Forces, Volume 12