CALCULATIONS OF RELATIVISTIC CRYSTAL-FIELD CONTRIBUTIONS TO THE ZERO-FIELD SPLITTINGS IN 4€ AND 34 ION COMPLEXES J.A. TUSZYNSKI Department of Physics, The Uni ton, Alberta, Canada, T6G 211 JM, DIXON Depa Warwick, € cvs TAL, Uk Reveivod 24 Augw ted by examples in State fons (eg. M 1, Introduetion Relativistic effects have conventionally been incorporated i theory using the idea of effective operators. Wybourne | applied the method of Sandars and Beck crystal-field y years ago, crystal-field operator Hey = D AUC, a by an effective op nen Jativistic states |snt) were the same us those of Hep bewween r i states |sfn). (sljmn\ He. |st" @) JA, Tuszyishi and J.M. Dison J Zero field splivings Fond 3 ian complexes ‘The relativistic states are related to the non-relativis and f=, This effective operator H. combination of double tensor operators (DTO's) W* orbital rank &” and total rank & Hay = SD Abpliere wees 2. The effective erystal-field Hamiltonian ‘The method discussed in section 1 does not account for the relativis ‘er of those parts of the electron-electron interactions which give ri crystal fields. In order to incorporate model Hamiltonian which includes Breit-P: is comprised of a | paramagnetic ion and a non-magnetic ions produeing a crystal ficld with a certai its Hamiltonian can be written as Sy fd tae “Savy yfi teed Ho Bae eS 5 2 We denote sites by A, wand electrons belonging to tc A we deseribe by iC A), ie is well known [3] but has basical mn. The first term in the square bracket of e ivistic Coulomb repulsion between electro terms are the familiar Breit-Puuli operator involving 1e matrix These interactions have already been investigated in detail by Armstrong 5], who derived operator e: ts for the three terms in question. Howev Armstrong's work (4, 5] referred to atomic systems centered about ane s whereas we use a similar formalism to incorporate other sites. Pollowi Armstrong [4] it was straightforward to find the equi eryst operators [6] for each of the terms in eq. (5). The non-relativistic Cou term yieldsU2 SLA. Tszpisk und JM, Disa 1 Zeros splings in $f and 3d ton compiexes ween, =F Ale 0) are the usual Lis a 9p-symbol, [k]=2k +1 and RS th jj’ equal to + Jor f~ $, being the angular moment of the particles. This term is identical with the result obtained earlier by Wybourne [1]. The coefficient A%(1) can be found in ref. [6] "The operator cquivalent to the second term in the intera be written as [6] HQ= > ALAR IW, 6) n of eq. (5) can where the effective operator coe! Dw’ )4)= o and the coefficient characterising the exystalline environment A¥(2) can be found in ref. [6]. It follows that £ must be odd and also (k’ + &") must be odd, but & may be both odd and even. The same co ims also hold for the third Interaction term in eq. (5). The equivalent operator inthis latter case may be written as HQ = S abayps(eeryewens + 4H where the effective operator coefficient in this case equals [6] ay L.A. Tussyiski and JM, Dizon / Zevosfeld rings in Af cal 3d Jom complexes 827 ‘and the coefficient AS(3) can be found in ref. [6]. The relativistic erystal field, therefore, is = superposition of the three contributions HAG) + HG a2) Assuming that phenomenological values for AS may be found from experi= ment, in particular from optical spectra, we can estimate the relative import ance of these three terms using eq. (3) with no restriction imposed on =k’ +k'+ k, The part corresponding to m even and k’ + &” even is exactly that of Wybourne [1] and is derived from the non-relativistic Coulomb interac- tion. Those terms corresponding to 1 odd have been recently discussed (6. 7] and found to be several orders of magnitude smaller than those with 7 even. The approximation made to obtain the corresponding crystal-fickt-like com- ponents consists in averaging operators over states located on sites neighbour 1g the paramagnetic ion. This then reduces a two-body operator to an ‘tfective one-body operator with the symmetry of the host, in the same spirit as the concept of crystal ficld was frst arrived at. When this becomes bused on the relativistic Hamiltonian, the tensor ranks in the effective operator wi almost the entire range of possible values, However, in the non-relat In most of them are absent Thus, the inclusion of relativistic effects involves both the use of relativistic (two-component) wavefunctions and the Breit~Pauli operator in the Hamilto- results in-new combinations of runks (k’A")k in the effective importance is tefl ide of the coefficients D,, Dz and Ds. In the non-relativistic limit, integrals R', tend f0 the well-known non-relativistic values (r*) and the D, coefficients reduce to b[M(OK)A] of ref. [8] which are ol iets of erystal fickd ‘operators (sce eg. (13) of the present D, and D, will vanish since the sm integral tends to zero. Consequently, effective crystal-ield operators. As has been recently pointed out [7] some of these new ns of ranks include those for which 1 is odd, These jeular operator equivalents have non-zero matrix elements between a {ground term a us excited terms, Their magnitude, however, is expected to be almost negligible. cover 3. Matrix elements and selection rules for one-body double tensor operators It has recently been pointed out [9] that all irreduci be classified according to their parity and time-reversal properties ther9a J.A, Tuyo wl uuxial or polar, This implies that a generalized DTO should be defined using extra orbital ranks k,, and k,, as BC { RY WEEts = PHYS) x [TEL x TOKE) 3) where (k) = & (Keiko), 7(S) is an axial irreducible tensor operator (ITO) acting in spin space, T"(L) is an axial ITO acting in orbital space, and T(E) is a polar ITO acting in orbital space. This means that, in fact, to cach standard DTO with ranks k,, k, as in eq. (4), there corresponds « number of generalized DTO’s whose tanks are ky, ey and Kay. Kay Such that {ky ~ Kol = ky < ka, + Kay. This allows the generalized DTO to assume all possible parity and time-reversal signatures. It has been shown [8] that within a hell these extra terms are indecd equivalent and do not offer any nc However, they are necessary in order to describe configuration interactions. In ‘the latter context they are equivalent, ey in eq. (19) is unchanged and is equal to the rank of the ery while k, may be zero or unity. A. similar argument applies to 1 Consequently, the resul Hermitian conjugation, e rank restrictions on tensor operators as has recently been elaborated on (7) However, from time reversal and parity considerations we can obtain selection fat orbital rank &; may either equal ks, oF ky ¥ 1 ‘rules for matrix elements of these generalised double tensor operators, namely (8) AL, (ie), 8) = stl] WIS = [ee (sy where A(T, 1’, k;,) is 0 when: either (J+ 1" + ky.) is odd of ky, =0 for 14, and A is 1 when (/ +1’ + k,.) is even. Thu & DTO which makes the configuration mi We infer that: (1) parity reversal results in the requirement that f different than 0 and such that (ky, ++’) is an even che polar orbital component of ing possible. yy must be w) |k tb) |t- (©) Ue Ul shy (@) 0%k, 62! Furthermore, itis straightforward to derive expressions for the matrix elements of DTO's, ee JA. Tszyhski and 1. Dison Ze 1s in $f and 3a Fon complexes 929 In one-particle configurations, therefore, the one-body part A 1, C,) of the effective Hamiltonian #.,, has the following reduced a's!) =D Fin, {kK}, YOUR DER, J H'1 te xfE Ekle) jfk where F denotes the following radial integral involving single electron hydro- genic wave functions P(r, fr) Pot) = | ier PORT POE rae, (15) part of f(r,) whi corresponds to the tensors wil ranks {&}) Fall expressions of matrix elements within pure and mixed configurations as well as between different configurations are available in the literature [8] 1. Examples of zero-field splittings We wish to investigate the role of relativistic contributions to crystal fields and hence to the zero-field splittings (ZPS's) of a number of ions, non-S-state and S-state. The energy of « particular M, Kramers doublet i presence of an axial erystal to first order is given by Fy = (L8IM,| AyD. we 21 ESM) a7) Assuming that Mj and MY refer to the outermost doublets of each particu system AE will be evaluated using SE = By, ~ Buy (1s) in conjunction with the Wigner—Eckart theorem, ‘The most complicated situation occurs in S-state ions where numerous cancellation effects result in very small values of the ZPS [11]. The most thoroughly investigated ion appears to be Ga", 4f° *S,,.. In the lanthanide ‘ethylsulphates (LaES) the ZFS is dominated by the axial spin-Hemiltonian