Physica 127A (1984) 28-240 North: Hol ‘THE THEORY OF SPIN CORRELATED CRYSTAL FIELDS LA. TUSZYRSKI*, IM, DIXON" and R, CHATTERJEE, Physies Department, The University of Calgary, Calgary, Alberta, Canada, T2N INt Received 2 Desember 1983, rail integrals. Second order degenerate pecturbation tofind ay equivalent operator which acts oly within 1, Introduction : ory of electron paramageti one of the mest dificult problems i the theory . .nce (EPR) has been the explanation of the spectra of S-state ions, Due to cha e orbitals all diags fo charge conjugation symmetry of the valence ‘ fe of spot and crystal field interactions, for pure LS states, must have buen observed tnd con 8 are not wel 1 H= i+ a Gi ral interaction Hes; (v) other Me stone ‘The nonvanishing me niversity of Newfoune! 1. Canada. om: Department of Physics, University of Ws ick, Coventry, CVA TAL, UK. 097%-4371/84/$03.00 @ Blsevier Science Publishers B.V, ‘THEORY OF SPIN CORRELATED CRYSTAL FIELDS 229 Teviewed so far were one-body mechanisms since none of them included Ho. However, Rajnak and Wybourne”) considered a second order perturbation ted configurations via Her an Correlated crystal field interaction. For a mn of these mechanisms the reader is referred to Wybourne') and. Buckmaster et al.) Newman’) suggested another method of generating a matrix element within the ground state of an S-state ion by following the idea of Rajnak and Wybourne and using an exchange-mixed crystal spin-correlated crystal field, Vsccx. Judd’) followed the idea of Newman and Presented @ scheme to generate an equivalent operator of the augmenting the crystal field tensor (C4), by a tensor of the f where cy is a parameter for a particular rank k. This mech: ly implied that ¢, <0 for the contraction of the radial wavefunction to correspond to similarly directed spi Dixon and Chatterjce*) henceforth referred to as DCI, derived an expression for the reduced matrix element of a spin-correlated crystal field operator. In a second paper Dixon and Chi d to as DC2, suggested # specific mechanism which would provide the effects described by Newman’) and Judd’) In a recent paper Newman et al.) referred to DC2 and stated mechanism of DC2 vanishes identical spin-sextet excited states of Gd within the ground configurat of Newman et al. also suggested that mechanism of DC2 would not vanish, is paper not necessary to multiply the final factor suggested by Newm 's Were present in the states The purpose of this paper is to generalise the mechanism of DC2 by including coupling to excited configurations. The approximate method using closure properties10 LA. TUSZYSSKEI et a 2, The perturbation method term so we follow Stevens') and define our unperturbed = LEP, 2 where E, is defined by B= Dining /S where |n,) denotes a particular spin-orbit mixed many-clect from a term with an orbital angular momentum E and spin S. P, operator for the manifold of states [n,) defined by P= > Indn,) . ® whether they are associated with diffe has been discussed at length by Stevens*) this way is so that Hy contains all the rotational symmetries of H. Note also that because of the way the projectors are defined, an operator P,OP, can have matrix elements between different states within the r manifold A unitary transformation is now performed on the Hy+ eV (where eV = H~ Hi) so that it becomes (Hot eve. X In now chosen to reduce all terms coupling excited states and the ground ttate to at least O(c”). The condition is PooxplieX)(Ho + eV) exp(-ieX)P, = O(e?), 6) ‘THEORY OF SPIN CORRELATED CRYSTAL FIELDS 231 where r#0 and leads from V, which acts only Vi= ePyVPo~ We are particularly interested in the second order terms. The states |ns) are all orthogon: states |n,) with r¥ 0 so, as the states |n,) are eigenstat Hy. Hy will disappear in second order, since PsP,P, where P, arises from Hi, is wal 10 PoP, =0, when applied to any s reduce to 3. Spin-correlated crystal field ‘A particular perturbation mechanism we intend to focus on employs %, as the numerator of eq. (7). The summation includes all the states belonging to the following configurations: one-body op time. Note that complete set: T= PAD Pet ®2m LA. TUSZYNSKL ot a. case eq. (7) can be written as _ sy Port Ha)P(Hee+ HePa © z TPA . ) where we have dropped volving the projector P?. ce the excited mani ively narrow energy band we ‘Tuszyfiski") and take out from the first term in eq. (9) an average energy difference J and replace Srvo Pe using eq. (8). We obtain AE =~ 2 PH gHesPo+ POH PaHlerPs + PoHerPyHecPa} +2EG- “oHeeP}HeePy + PoHcsP:HeePo} Here 4, = E,~ Fy and only cross terms between Her and He. have been retained. Those involving He: Her wil tain spin and H.: H,, will be rotationally invariant. We now consider each of the terms in turn: 4) PoHcHesPo. Wi the (nl) configuration we write Hey in the usual way as a may be written in the second quantised form as MECN PQ) adnan, where each aj,- creates an ni-electron with magnetic quantum number m and spin o. Summing over the spin components and picking out exchange con tributions* we obtain ‘THEORY OF SPIN CORRELATED CRYSTAL FIELDS a the four and we have taken only the leading tem in the exchange (which means setting n'=0 and n =n in the orbital operators ofthe appendix). Therefore, exclud: ing three-body terms we represent the equivalent operator for part (i) ofthe spin correlated crystal field mechanism as View= Dat (SS), ay where wf = —Q/A)BKI and Viccr acts entirely within [0)) AE Seco = (O1Viccr!) (18) where ABccr denotes the contribution from part () towards AF of eq, (19) ii) PoHePoHer! s second term in eq. (10) is small and may be ignored in ha since the crystal field part of it vanishes idemtically for pure LS charge-conjugation symmetry. PoHeeP}HesPo. is third term of eq. (10) has been calculated in the appendix and reducesau JA, TUSZYRSKE ota to its operator equivalent form Vicce= Dah E CHOS-S, a9) where SBE _ IK “NIME Pr eel = (3 FS) on en Here we have defined the following parameters: 2 Rial n'y ey and . Pane = | VOM? Ar @ @3) where = t+ yl. Following DCI we transform eq, 3) into a tensor product kT 2k+1 Vocer= Eat 3 [ech x six e% Using the double tensor representation introduced by Judd) we find es) ‘THEORY OF SPIN CORRELATED CRYSTAL Fi 28 and (Cox sip = BORK WE, ) where the equivalent operator coeflicient b(1kk’) is ko Keer sarey- coms § i) YF} vSS MEST Hers ya en Therefore, we write Vier a omy es (of matrix elements, ‘The following matrix element of zero-field spli be of great importance in the calculations gst T= (U5 1E aM Vecer| 2b") @) In order to evaluat the reduced mat we first apply the Wigner-Eckart theorem to separate yent R from the projection-dependent of een E (iy 6 ae) Ro 0) where OO Sr wenden, ayers) on Replacing the summation over particles by the use of many-partcle operators, wees, @26 LA. TUSZYSSKI eta. lund using the appropriate expressions for reduced matrix elements of product ka (wren S coramyvxeTT = (eK 3) operators in eq. @3) and the reduced matrix elements of V# have been tabulated by Chatterjee et 4 Conclusions In this paper we have provided a detailed derivation of a mechanism producing a spin-correlated crystal field. We have generalised previous studies by including the effects of in thin excited configurations. We have also given a is of the equivalent spin- eld operator. be used to interpret the zero fleld Janthanum ethylsulphate in a tater paper. ings of Gd in Appendix In this appendix we analyse the perturbation elements Hep and H,, as perturbation operators we schem: (LY Heal (lt PX Tern) ‘THEORY OF SPIN CORRELATED CRYSTAL FIELDS, 237 A. complex conjugate elem: annihilation operator for an ‘The above matrix clement and its complex conjugate can arise in the four second quantised operator products: 1) PobraiaasP.aibsPy, 2) PoatbraaP.aibePo, 3) PebsasPaiatbyasPo, A) PobsaPraraiachsPo te quantum numbers for excited state projected out by P, Suppose nj degen (0)) and and 4 are fixed. Then a%byln) is an excited state which rst appear in the manifold r because of the way His constructed (Stevens), From nj) we can generate other states in r by choosing the four nf quantum numbers appropriately and all's. Si ‘we can operate on |n), another Iehere Pe 3, Inn. Thus, case 1 involves a) |nsXni|biaiaa: by operates on a fixed [ni it must produce one and only one of the n of the eigenstates of He, Hence, 4) is either 3 zero depending on whether az is already present in {r) or not (bp will always be able to destroy an n''-electron since the nl’ shell is filled inn). ‘When this matrix element is unity the above becomes D lnoXnal ndaaibylniXni) where 3’ denotes that the summation is over all states jn3) and \n) which give nonzero matrix elements. Note that the summation over f now disappears. If we remove the dash from the summation sign, then we obtain ) PabtatasPn LA. TUSZYXSKI which has nonzero matrix elements in the same posi dash. Furthermore, this latter expression gives zero matrix same place as operator (a). Thus, expression (a) reduces to (b). ymmuted through to the when b operates on any bib, = 1 ~ 6,63 and the pair of b's reduc ©) PoatazasaiPs. in the ground configuration (ni). ‘The operator in (c) acts only 1 cases 1-4 reduce t0 (b), bt can be of By, If a B then 6; and bp anticommute in Po, (0) gives zero. When a =f to unity and expression (b) becomes aur Pos » mgmt] Halmins enter) pai, ayn AinPs 2 . ELH ayia ny 9 4 where 4 denotes the energy separation: 4 = E(w for cach once ‘quantum numbers for given by m,. The operators ofa" aa" a, The resulting products tour types which, following Stevens", can be ws angular momentum operators Gx Am =D AnmnlOn ns: Gindyt =F daw slOPa iy Ane = 3D Ann Org AAVCL = 25 42s.) Gigs de = Sel Oe Elly) ‘The magnetic and o (A2) (A3) as ‘THEORY OF SPIN CORRELATED CRYSTAL FIELDS 2 al operators efficients N,. are cither O§ or OF from these pairs, m = min eqs. (A.1)-(A.8) and the operato ‘1-4 can be rearranged to give > menos Vscce=-4 D We then find We require i j since other ‘obtain a pure ise we ly orbital oper SiS) = 3/4. The underlined comp o require that n°=0 and (8) as we are wholly )). The angular fe coefficients (Avs + Byx), which in the case yen m)(-m mom m) a 23) ay cm, 0 omy Kem, 0 my20) JA. TUSZYRSKL et = EI, mins mdm meeim me) Cone Onder ns) whereas, if "= 3, they are 4022 (Cn mem ma) (em om) (aan Bor EE cree(G, m) 30233 23 (Con 0 meme 0 (ara)