L02-Atomic Spec-01.pptVIP

Lecture 2Atomic Spectroscopy-1 An important effect of electron repulsion is to remove the degeneracy of those orbitals which are degenerate in the hydrogen atom, to give a set of orbitals: n=2→ 2s, 2p n=3 → 3s, 3p, 3d n=4 →4s,4p,4d,4f…… The orbital energies Ei vary not only with the principal quantum number n, as in the hydrogen atom, but also with the orbital angular momentum number l(l=0,1,2……for s,p,d…orbitals) Pauli exclusion principle No two electrons can have the same set of quantum numbers n, l, ml, ms Ml can take 2l+1 values and ms=±1/2, so an orbital with quantum number l can take 2(2l+1) electrons s, 2; p, 6; d, 10 and so on. The energy order of the orbitals The difference of configuration and state A configuration describes the way in which the electrons are distributed among various orbitals; a configuration may give rise to more than one state Total angular momentum j Magnetic moments:orbital, spin,nuclear Coupling of Angular Momenta Two types approximation Russell-Saunders Coupling(a) Non-equivalent electrons Non-equivalent electrons are those which have different values of either n or l , for example, those in 3p13d1 or 3p14p1 configuration are non-equivalent electrons; while those in 2p2 configurations are equivalent electrons. Coupling of angular momenta of non-equivalent electrons is rather more straightforward than for equivalent electrons. ll coupling:two non-equivalent electrons, 2p13d1 Electrons in filled orbitals give no contribution to the coupling, because L=0. Therefore, the excited configurations of C 1s22s22p13d1 Si 1s22s22p63s23p13d1 Of C and Si both give P,D, F terms ss coupling S=s1+s2, s1+s2-1,…|s1-s2| In the case of two electrons this means that S=0 or 1 only. The magnitude of resultant S is : LS coupling There is appreciable coupling between the resultant orbital and resultant spin momenta. This is referred to as LS coupling and is due to spin-orbit interac