SPIN-CORRELATED CRYSTAL FIELDS: A STUDY OF TWO-BODY AND RELATIVISTIC EFFECTS FOR Gd?" IN LANTHANUM. ETHYLSULPHATE, JA. TUSZYNSKI Department of Physic, The U J.M, DIXON Deparn of Physes, The Univers Received 14 tune 1988 incorporated ofthe SCCE sw lensoria he very 2] th nteractions [3, 4] eo it complexes. producing crystal fields of various point symmetries. In particular, for Gd in ethylsulphate (LnES), on-site mechanisms calculated to high orders of pertur- bation theory [1.2]. together with produced a ZFS which was approxi lations involved excitations to other contributions lely tWo times too in-conjunction with the projector method of Stevens site contributions [3, 4] on the other hand, arose from exciting 0378-4371 /84/$03.50 © Elnevier Sclonce Publishers BLY, L.A, Tussyrski and LM, Dison 4 Spin-corneated enya fi ie: Gin LAS 53 Afelectrons of Ga"* to just unbound” 3s: surrounding 11,0 molecu could use operator we states localised neur the ¢ tricapped prism in LnES, These excitat ‘¢ Coulomb repulsion alone even though they themselves ance. This is because exciting electrons to each 's in turn produces an effective anisotropic metry of the compound, There are a number of feraction anisotropic two-body operators xd (6. 7], whether the not [8,9]. There are six such mechs operator a where the 0"! operators are t electrons and 4, is the respective two types involve excitations 0 another site (der below (A) HCI x10" G) x OM AD and (I) YCI]E x LOM) x OMENS) -al_harmonies. ist of these operators is overal the second is isotropic. Some of these five types of two-body ike operators can be shown, in fact, to give id matrix elements to an SCCF operator of the form despite the fact that this operator contains spins [11]. In ref. & all the effec! yperators obtained by the method of Stevens were cast in an orbit-orbi relativistic interactions like those above may be. repre- (ensor operators [12, 13] either one-body WY" or “PPdt bea bdeibemsl Bhssslea Mesbebieteicnn Pitade doce04 Ga! in Lats twosbody [8 ‘A number of interesting physical examples can be found to illustrate | second-order spin-orbit: spin-orbit mechanism yields ky, = kis =1, or a second-order relativistic-erysta-field spin-orbit mechanism yields &, 1. Ky. = 3, Ba, = ka = 1 ‘One of the objectives of this paper is to reevaluate the matsix elements of the SCCF operator using exact two-body matrix elements provided in ref. 8 This would enable a more accurate estimation of the ZFS for Gd** in LaES. One could compare these more accurate results with the approximate method adopted previously (1, 2] where matrix elements were reduced to proxtucts of ‘one-body type. Another objective is to incorporate relativistic effeets into the SCCF operator by using the relativistic radial exchange integrals [14] to complement our previous calculations using ie tworhody SCCF [2]. This woutd also illustrate the many tensor products shown to exist in the iNonians of erystal field complexes [8]. Tt has becn argued recently [15] that for a one-body double tensor operator WO?" the restriction that (k'+ Kk) should be even to preserve Hermiticity is unnecessary and, consequence, operators with ranks such that (k' + &”+ k) is odd should be ied in the Although we later find that making the SCCF operator relativistic produces very small changes in the ZFS some of the largest contributions arise from two-body components with (ky, + k,y + K,) odd and (kay + hes + Kz) od ‘We have recently shown elsewhere [16] how intersite eryst incorporated into an effective operator formalism, and also jstie by including both Coulomb and Breit-Pauli terms in the interaction between clectrons on different sites. In this paper, however, we we a two-body contribution to the relativistic crystal field, namely the SCCF interaction made felativistic. To emphasize the important difference between orbital operators ‘with angular momentum arguments and those whose arguements are angles, all the derivations are curried out using the former operator set fields may be 2, Relativistic one-body crystal field operators Relativistic effects can be incorporated into the crystal field through the use of effective operators. The idea is to find an effective operator acting J.A, Tuszyriski and 4M. Dizon | Spin-correlated crystal fields: Ga*- im LnS 305 nonrelativistic states |sfjon) which will of the crystal ficld within relativistic sta Sandars and Beck [17] was applied by W nonrelativistic crystal ficld operator 1c identical matrix elements to those fim). The method developed by ne [12] to replace the standard Hep => ASr’CX(0, 9) a) by an effective Hamiltonian which may be wr Me @) = S atpiwenn where W's a double tensor operator with spin rank A”. orbital rank A” Coupled to form a resultant rank . The coefficient D[(R’#)K| in cq. (2) is found to be given by [12] het Fee 9b) 94a yb an | aya f ren. tegne, « where F and Gare respectively the large and small components of the Dirac equation and j and j’ are J+ 3 and [—3 for particles with orbital gular momentum 1. The above result holds providing the effective operator acts ‘vithin one electronic configuration [and the arguments of Care the same as those of spherical harmonics, Le. 6 ¢ For Gd" in Ln the crystal fek! coefficients are [ Ap=160.7em!. — AS=~307.2em™" and the relativistic parameters D[(K'K')k] have been tabulated in table T following refs. (6] and [7]. It is well known [19] that spin-orbit coupling plays a major role in a number of mechanisms which contribute to the ZFS for Ga in LnES. For this reason it is convenient not to se the pure LS-term states ['S),06 ris unl JM, Dison / Spincorrl stl fields: Gd" in LES The valves of relativistic pu DICKY] for Ga" in THES. sd [7] «KE JP), ete. as a basis set but rather spin-orbit mixed states, ive. tho ‘obtained by diagonalizing the spin-orbit operator among the terms “Thus, following Wybourne [12] we have the spin-orbit mixed ground expressed as °sy = 0.9866)*S) +0.1618)"P) + (-0.0123)|°D) + 6. 0,00014)°G) ++ ©) tude of the ZES due to the jon theory &s With this we can calculate the mag crystal field in the first order of pertur AB ger = Exes = rian of eq, (2) and the term in the square bracket comes from the Wigner Eckart theorem and has been tabulated in table VIT of ref, (20), In tuble Hl we have 1g matrix elements and we have used the prime number notation to represent the result, The magnitudes of the ZFS for most of the terms are very small (less than 10°” em!) except for three, ic those with ranks (02)2, (11)2 and (13)2 which yield +0.112¢m_', ~0.142em and +0.00L em‘, respectively. Thus, due to partial cancellations the overall first order one-body contribution to the ZES is small and amounts to only =0,029em"! which is of the wrong sign and approximately 10% of the magnitude of the experimental value of +0.236em [21]. 1A. Tiszyikt and 1M. Di hte LL “The values of all the ZES mechanisms due to 3, Nonrelativistic spin-correlated crystal fields In this section we derive the matrix clements of a nonrelativistic SCCF at use exact two-body matrix elements which have been given i compare these results with those of jxon and Chatterjee {22}. We begin by w