Download Structure and Bonding, Volume 2 by D. Wales, R.A. Christie, G.E. Ewing, B. Jeziorski, K.D. PDF

By D. Wales, R.A. Christie, G.E. Ewing, B. Jeziorski, K.D. Jordan, K. Patkowski, K. Szalewicz, S.S. Xantheas

ISBN-10: 3540039899

ISBN-13: 9783540039891

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Extra resources for Structure and Bonding, Volume 2

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Kramers Doublets As a p r e l i m i n a r y step in t h e construction of t h e K r a m e r s doublets we shall c o m p u t e the s p i n - o r b i t coupling m a t r i x w i t h i n t h e t2-orbitals 4, ~, ~. T h e e-orbitals do n o t e n t e r into t h e discussion since t h e y are presum e d to be far r e m o v e d in energy, as evidenced b y t h e fact t h a t hemoglobin azide is a low spin c o m p o u n d . T h e p e r t i n e n t p a r t of t h e s p i n - o r b i t coupling o p e r a t o r is given b y (7s) 7.

With this information we may list all the possible electronic configurations without regard as to their energies: (3d) 5, Fe 3+" t~, t~e, t~e 2, t ~~e ,3 t~e 4 {3d) s, Fe2+: t~, t~e, t4e ~, t~e 3, t~e' These configurations together with the spin alignments corresponding to the maximum value of S are shown in Fig. 20. ),(3df % F--F-] Fqi-q ~ FTWE t~9('A~) t~geg 4 eg25(T2g) t2g :5 eg3 t2g 2 eg4 t2g S=2 S=l S=O S=I S=2 Fig. 20. Occupation of t2g- a n d eg-orbitals in ferric a n d ferrous systems. listed above gives rise to a set of terms consistent with the Pauli principle.

56) and the third is based on the d-orbitals (Eqs. 4). [aT2 E * c t ' > = ~ - [2T2{ 0 > - - (~)t ]2T2 - 2X 1 > = r f1 It, 0+ > - (w it, 1- > = r 1 [12+ > - I - 2 + > ] IZT, E" 13" > = (-~)t i,Tz 89 _ 1 > = (~)~I t , - 1 = -- (w I'T2 U' • > -- Izrz ~- 1 >--V*-It*~ x V3- I h - = V3x I1+ > = 0 > > 1 > - Vo- [[2- > - I - 2 - > ] = -- V~ r'T, 89 -- 1 > -- (w ----- I:T2 U ' X > + (~)~ I - l - > ]+ > - - (w I'T2-- 89 0 > It* 0 - > wx- [[2- > _1_2_ > ] I~T,-- 89 - - 1 > = I t , - - 1- > =-11-> 48 M. Weissbluth It2 1 + > = 12T2 U ' v > ....

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