yen 143A (1987) 331-345, ‘Holland, Amsterdam ‘A STUDY OF EFFECTIVE CRYSTAL FIELDS, SPIN-ORBIT COUPLING AND RESIDUAL INTERACTIONS, DUE TO RELATIVISTIC EFFECTS AND CONFIGURATION MIXING, FOR Gd’* IN Cy, SYMMETRY L.A. TUSZYN Department of Physics, Memorial University of Newfoundland, ‘1 Toke’s, Newfoundland, AIB 3X7, Canada and JM. DIXON work, Christodoulos et al") have made a qualitative estimate of ZFS for Gd'* which is brought about by Inter-tite excitations to s-ike states close to neighbouring oxygen ions. These Iculations give ZFS which is opposite in sign to that of Tuszysiski et 0978-4371 /87/$U3.50 © Elsevier Science Publishers B-V. Physics Publishing Division)92 LAN TUSZYNSKI AND LM, DIXON EFFECTIVE CRYSTAL FIELDS AND SPIN-ORBIT COUPLING 333, ns is a ZFS close to thas al2) and the net result of the two cont experimental value. This agrees with physical in neglected this field is written in terms of spherical tensors then the even-rank coefficients B”,, inter suxpected for many years that other sites are involved’) and ZES has been polated from parametric fits by Wybourne’*), are found to be ‘observed for Gd" in other hosts of the same symmetry which are oppo sign”). The work of Tuszyfiski et al.'") involved e3 ns on the site of the Gd" ly and used a two-body spin-correlated crystal field operator of the BR=200em™', BL =—S8em By =—S50em™', BE= 50cm, + istic wavefunctions were used to calculate wo ie mechan- Heaeeeent «where-we have not considered ed-rank eoefcens nor the Mase term deme) Estates of the apinorbit constant range from 147Dem"" according 10 ‘of orbit-orbit and spin-orbit interactions Newman and Urban’) to 1717em™! quoted by Abragam and Bleancy'*) -body relativistic mechanisms whereas Wybournc’) used the value of A= 1480em ', W this Sie for oor ealclatns and wie: V,yAL*S. Tus, our starting Ha caystal eld content by nian becomes ‘and Beck”) and developed by "The basic dea it replace an wens aessSphchamev operator O whi |g.) and [W4) by an effective * Bacay ° Sperator Ogg within the space ofr ;). We ake the Kinetic energy and a central field It is convenient to use the one-body double tensor operators W Armstrong”) in which case the perturbations may be written in terms of will produce two-body spin-correlated crystal beer considered in carlier work"). We will, therefore, consider the rem: the crystal field and spin-orbit. Firstly, these sill be written as le tensor operators. These one-body tensor Chea aTOWO" and LoS =309344 operators will then be c operators using the well-known prescription’) and perturbation theory carried out to second order to produce an effective operator within the ground configura Chm -0.6738W", Cy = 0.80570" where 12 ) and (7°*) have been incorporated and given by 2, Structure and pretiminaries (P)=0.785 au, (r°)= 1515 au, (4) ‘Lanthanum liphate (LaES) has the chemical formula (r®) = 6.281 au., (9°) =8.35 au. Ln(C,H,S0,),°9H,0 and the Gd" ion enters s a tanth- amide’ ion, The structure of LnES has been determined by X-ray scattering We have techniques by Katclaar™?) and Sinha'*). ‘The nine HO molecules form @ and found trleapped prism around the central lanthanide ion, The met Id components also cher for al simplicity sour been extrapolated for Gd'™ from other lanthanides fne*) and mak ce being 2.59 A and the six distances to the prism co jons 7.10 A apart along the c-axis and o the point symmetry about the Ln site is Cy, If all but the nearest oxygens were Tg a ()oy JLA, TUSZYNSKL AND ILM, DIXON whore Dk kak) = (IT DD kad Lik eR IMGT ele xtarIlh 6 1! } ‘ . © me ais where [k]s2k +4; jf Patt tod (: 52) is a 3j-symbol and ] is a Gj-symbol. If we denote j= 1+ iby “+” and j= S by "=", then Ry, are defined by Rt, = | Mot + Gur, ai = [RF 46,6 Jar, fo) RL =| AUR eG? ar, where F, and F denote the large component for j=!+4 and j=!~ 4, Femectively, and G, and G- have been defined analogously forthe small pomponcnt. For example, PC? pain? + DCW"? + DE)", (s) where the coefficients D( kjk) can be found in table I. It can be seen from table 1 that D(@22) is larger than D(112) and D(132) by two orders of ‘magnitude. "To replace the spin-orbit coupling we follow Tuszyfiski™”) and perform the following calculation: rower > plkKo)Wwe” 9) where the coefficient D is, 2k , wait) Blea tie x(} ; ‘}j730 9348, (a0) EEVECTIVE CRYSTAL FIELDS AND SPIN-ORBIT COUPLING, with R;? being defined by putting k= 3 in eq. (7). The results of the replacements in eqs. (5) and (9) are summarized in table 1 \. Perturbation theory To incorporate interactions with excited states we use standard perturbation theory with V=V, + V4, where Y= & afb) Dk kw an represents the relativistic crystal field and v= > wptkkoyw? «a2 represents relativistic spin-orbit. We have used o(k)=BU/(r*) and w= 30.9344A/(r7"). Hence, our effective Hamiltonian, excluding %, and the effects of C8, becomes a3) where the summation over 1 includes all excited states both within the ground 4f° configuration and excited configurations. For the ground configuration we