19.2 Atom-Atom and Atom-Molecule Seattering 19.2.1 The coupled equations In the previous section we discussed the general quantum mechanical ‘treatment of scattering of a particle by a fixed potential. Necessarily this treatment is only appropriate for elastic seattering,and oven then it ts only appropriate for one and two particle systems. Here we will consider the procedure for cases with at least three particles. For example, starting with Hf atom and a fast proton H <—_______ i" the products may be (i) slow H and fast H (i.e,, elastic scattering) (ii) slow H* and fast H (charge exchange) (is). stow or fast H in an excited state (clectronic excitation) and an H* Gv) two protons plus one electron. In 87.1 we found that the exact wavefunction for a molecular system can be written as (x, R) of®) Dl B) a) where ¥;, the electronic wavefunction, is an eigenfunction of the electronic Hamiltonian My = BY ®) ‘The Schrédinger equation in this case is RO, = FxOxor equivalently (f= Ey) 0) = 0 @) for all i. With tho Born Oppenheimer approximation we tale the different atatea of the molecular system to have the form of a simple product, O40 R) = Figc(RII, (0, R) ® In this approximation there are no transitions between different electronic states. This approximation is most likely to be a good one when the electronic energy curves 5, are widely separated. In the case that two electronic states, say ¥, and ¥,, have similar energies for same R, we expect a strong coupling between these states requiring a wavefunction of the form Ox = Fix(R)¥,(r, R) + Fex(R)¥,r, R) (5) rather than (4). For a diatomic molecule with nuclear charges of Zs and Zp, the total Hamiltonian is « aap Fev et (6) where yan Letting obe the total nuclear potential and using (1) and (6), we obtain (Hy) Blo), = DOKI ge M+; ELEY), ®) where the integrations are over electronic coordinates only (denoted by sub- script r here, often the subscript will be deleted).- The V* operates on both FR) and we, R) leading to yIv ley = Lepr, +298) OM lEle +l ep SOR s BTN + IGF; ® where y= Olylep (10a) Jy = IVD (100) ‘Thus the Schrédinger equation (3) reduces to the coupled equations Le pan: 1 - ag, 9 VaR = BOER) «29 GE Tag" RFs + wyTigeD = © ay ‘There is one equation of the form (11) for each electronic state i and hence this whole infinite set of coupled equations must be solved in order to obtain the total wavefunction (1). since (ele) = 2B FFQVFR) (Y/¥), (22) =D |ryml=1 j