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Journal of Magnetism and Magnetic Materials 316 (2007) e346e348 www.elsevier.com/locate/jmmm

Magnetic properties of the geometrically frustrated spin-1 Heisenberg 2 $ model on the triangulated Kagome lattice
Jozef Strecka
rik University, Park Angelinum 9, 040 01 Kos ice, Slovak Republic Department of Theoretical Physics and Astrophysics, Faculty of Science, P. J. Safa Available online 3 March 2007

Abstract Geometrically frustrated spin-1 quantum Heisenberg model on the triangulated (triangles-in-triangles) Kagome lattice is examined by 2 the use of variational procedure based on the Bogoliubov inequality. The investigated model system has an obvious relevance in elucidating magnetic properties of a series of polymeric coordination compounds Cu9 X2 cpa6 (X F, Cl, Br and cpa carboxypentonic acid). A striking magnetization curve with the 1-plateau implies an appearance of compromised non-collinear spin arrangement 3 within the plateau state, whereas a presence of the 5-plateau with a collinear uud spin alignment cannot be denitely ruled out at higher 9 elds. The thermal variation of the susceptibility times temperature data exhibits typical features of the quantum ferrimagnet. r 2007 Elsevier B.V. All rights reserved.
PACS: 05.50.+q; 75.10.Jm; 75.40.Cx; 75.50.Nr Keywords: Heisenberg model; Triangulated Kagome lattice; Geometric frustration

1. Introduction The quantum Heisenberg model on frustrated planar lattices represents a long-standing theoretical challenge as it exhibits the variety of exotic non-magnetic ground states due to zero-temperature phase transitions driven by quantum uctuations [13]. Another striking feature related to the geometrically frustrated planar lattices is being the existence of quantized magnetization plateaux in the low-temperature magnetization curves [2,3]. It is noteworthy that this peculiar quantum phenomenon has already been experimentally veried in the prototypical examples of several frustrated quantum spin systems, such as the triangular lattice compounds CsFeSO4 2 [4], Cs2 CuBr4 [5] and RbFeMoO4 2 [6], the Kagome lattice compound [Cu3 titmb2 CH3 COO6 ].H2 O [7] and the ShastrySutherland lattice compound SrCu2 BO3 2 [8]. A series of polymeric coordination compounds Cu9 X2 cpa6 (X F, Cl, Br and cpa carboxypentonic
$ This work was supported by the scientic grants Nos. VEGA 1/2009/ 05, APVV 20-005204 and LPP-0107-06. Fax: +421 55 6222124. E-mail address: jozkos@pobox.sk.

acid) [9] provides another prominent class of insulating magnetic materials with the frustrated lattice topology. The magnetic lattice of this series constitute copper ions situated at two non-equivalent positions (see Fig. 1). Cu2 ions with a square pyramidal coordination (a-sites) form equilateral triangles (trimers), which are interconnected to one another by Cu2 ions (monomers) with an elongated octahedron environment (b-sites) residing the sites of Kagome lattice. Such magnetic structure can be best summarized as triangulated (triangles-in-triangles) Kagome lattice, since the trimeric units are embedded in the triangles of Kagome lattice. Experimental studies reported on this family of compounds have revealed obvious manifestations of the frustration effect. The compounds do not order down to 2 K [10], the magnetization shows a quantum plateau in a wide range of magnetic elds and it does not saturate up to 38 T [11]. On the other hand, the temperature dependence of reciprocal susceptibility indicates two temperature regimes inherent to two different exchange interactions, the Weiss constant amounts Yw 230 K above 150 K, while it decreases down to Yw 6 K below 50 K [11]. Based on the considerations of exchange paths, a stronger antiferromagnetic interaction has been assigned to the exchange

0304-8853/$ - see front matter r 2007 Elsevier B.V. All rights reserved. doi:10.1016/j.jmmm.2007.02.144

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ka J. Strec / Journal of Magnetism and Magnetic Materials 316 (2007) e346e348 e347

b a b

b a

ferromagnetic one is perturbatively treated within the variational mean-eld like treatment. Unknown variational parameters (laa , ga , gb ) can be obtained using the Bogoliubov inequality GpG0 hH H0 i0 , where G and G0 are free energies of the system described by the Hamiltonian H and H0 and h. . . i0 denotes thermal average over the ensemble dened by the trial Hamiltonian H0 . After minimizing rhs of Bogoliubov inequality the variational parameters read: laa J aa , ga 2J ab mb H, gb 4J ab ma H with both sub-lattice magnetization dened as ma 1 3sh3xga shxga 2e3xlaa shxga , 6 ch3xga chxga 2e3xlaa chxga mb 1 tanhxgb , 2 3 4

Fig. 1. A cross-section of the triangulated (triangles-in-triangles) Kagome lattice. Solid (broken) lines schematically reproduce the exchange interactions J aa (J ab ).

x 1=2kB T. The Gibbs free energy then follows from G=N laa =2 4J ab ma mb x1 fln2chxgb =2 ln2ch3xga 2chxga 4e3xlaa chxga =3g. 5 Eqs. (3)(5) provide a closed-form expression suitable for calculation of all basic thermodynamic quantities. 3. Results and discussion To simplify further discussion, let us dene a set of dimensionless parameters t kB T=J aa , h H=J aa , and a jJ ab j=J aa , as describing temperature, external eld, and relative strength of interaction parameters. Next, m  2ma mb =3 stands for the total magnetization reduced per one site and we shall set a 0:025 with regard to the suggestion [11] for the ratio between both coupling constants of Cu9 X2 cpa6 compounds. First, let us take a closer look at the low-temperature magnetization curve. Fig. 2a shows the total and sublattice magnetization as a function of the external eld. As one can see, the low-temperature magnetization curve exhibits a plateau in the range of moderate elds. It can easily be understood that the plateau at 5 of the saturation moment 9 corresponds to a spin conguration with the monomeric bsites aligned to the external-eld direction, while the trimeric a-sites rest in one of the available uud (""#) spin congurations (f1 or f3 ). As recently pointed out by Dai and Whangbo [13], the geometric frustration inherent in the triangle motif might possibly lead to a compromised non-collinear spin arrangement. In the absence of external eld, the four-fold degenerate ground-state eigenfunctions p f1 1=2j "#"i j #""i; p f2 1=2j #"#i j "##i; p p f3 2=3j ""#i 1=6j "#"i j #""i; p p f4 2=3j ##"i 1=6j #"#i j "##i; 6 can be mixed to obtain the four non-collinear spin arrangements shown in Fig. 3 that can be described by

coupling J aa between the a-sites creating trimeric units and a weaker ferromagnetic one to the coupling J ab between trimeric a-sites and monomeric b-sites with the overall ratio jJ ab j=J aa % 0:025. 2. Model and method In the present article, we shall aim to analyze the spin-1 2 Heisenberg model on the triangulated Kagome lattice in connection with the magnetism of the series of Cu9 X2 cpa6 compounds. So far, the geometric frustration inherent to this lattice topology has been studied in terms of the Ising model only [12]. It might be expected, however, that an application of the Heisenberg model would be more appropriate, since the exchange coupling between Cu2 ions is almost isotropic. Accordingly, let us dene the Heisenberg model upon the underlying triangulated Kagome lattice (Fig. 1) X X X H J aa S a S a J ab Sa Sb H S d i , (1) i j k l z
i;j k;l i;d2a;b

where S Sx ; Sy ; S z stands for the spin-1 operator and its 2 spatial components, the rst two summations extend over two different sets of the nearest-neighbor a a and a b pairs, respectively. Finally, the last summation runs over the total number of sites (3N) and this term incorporates the effect of external eld. Since the Hamiltonian (1) cannot be treated exactly for the Heisenberg model, in what follows we propose a variational procedure based on the trial Hamiltonian ( X H0 laa S a S a S a S a S a S a k1 k2 k2 k3 k3 k1 ) 3 Xh gb b i a ga Sz ki Sz ki . 2 i1
k2trimers

which takes exactly into account stronger antiferromagnetic interaction between the a-sites, while the weaker

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Fig. 2. Total and sub-lattice magnetization as a function of the external magnetic eld for a 0:025 and t 0:05. The intermediate plateau corresponds to: (a) collinear, (b) non-collinear, spin arrangements of the trimeric units.

Fig. 3. Four possible non-collinear spin arrangements of the triangle unit with the zero total magnetization.

hence, even small external eld changes the divergence to a local maximum followed by an abrupt decrease of wt to be observed nearby zero temperature. The position of this maximum shifts towards higher temperatures with increasing the eld strength until it vanishes above h % 0:05. Note that the aforementioned scenario is in a qualitative accord with the behavior of Cu9 X2 cpa6 family [10]. In summary, we have provided the magnetic data of the spin-1 Heisenberg model on the triangulated Kagome 2 lattice that brings insight into the frustrated magnetism of the series of Cu9 X2 cpa6 compounds. The magnetization curve of this system turned out to exhibit a quantized plateau at 1 (5) of the saturation magnetization with the 3 9 non-collinear (collinear) spin arrangement of the trimeric (triangle) units. The 1-plateau observed experimentally 3 implies a real existence of the non-collinear spin arrangement [11], however, a possibility that the 5-plateau emerges 9 at higher elds cannot be denitely ruled out. To the best of our knowledge, such fractional value has not been reported yet neither theoretically, nor experimentally. References
[1] G. Misguich, C. Lhuillier, in: H.T. Diep (Ed.), Frustrated Spin Systems, World Scientic, Singapore, 2004. [2] J. Richter, J. Schulenburg, A. Honecker, Lecture Notes in Physics, vol. 645, Springer, Berlin, 2004. [3] A. Honecker, J. Schulenburg, J. Richter, J. Phys.: Condens. Matter 16 (2004) S749. [4] T. Inami, et al., J. Phys. Soc. Japan 65 (1996) 2374. [5] T. Ono, et al., Phys. Rev. B 67 (2003) 104431; T. Ono, et al., J. Phys.: Condens. Matter 16 (2004) S773. [6] L.E. Svistov, et al., Phys. Rev. B 67 (2003) 094434. [7] Y. Narumi, et al., Europhys. Lett. 65 (2004) 705; Y. Narumi, et al., J. Magn. Magn. Mater. 272276 (2004) 878. [8] H. Kageyama, et al., Phys. Rev. Lett. 82 (1999) 3168; H. Kageyama, et al., J. Phys. Soc. Japan 69 (2000) 1016. [9] R.E. Norman, et al., J. Chem. Soc.: Dalton Trans. (1987) 2905; R.E. Norman, et al., Acta Crystallogr. C 46 (1990) 6. [10] S. Maruti, et al., J. Appl. Phys. 75 (1994) 5949; S. Maruti, et al., J. Magn. Magn. Mater. 147 (1995) 398. [11] M. Mekata, et al., J. Magn. Magn. Mater. 177181 (1998) 731; M. Mekata, et al., Can. J. Phys. 79 (2001) 1409. [12] J. Zheng, G. Sun, Phys. Rev. B 71 (2005) 052408. [13] D. Dai, et al., J. Chem. Phys. 121 (2004) 672.

Fig. 4. Thermal variations of the susceptibility times temperature data for several values of the external eld.

means of ci ai f1 bi f2 ci f3 d i f4 (i 14, the mixing coefcients are given in Table III of Ref. [13]). As a result of the non-collinear ordering, the sub-lattice magnetization ma does not contribute to the total magnetization which consequently exhibits the plateau at 1 3 of the saturation moment (Fig. 2b). This magnetization scenario is in agreement with the experimental data reported on the Cu9 X2 cpa6 series [11]. Naturally, it is in question whether the 1-plateau persist up to the saturation 3 eld (strictly speaking, the non-collinear order should exist just in the zero external eld), or the 5-plateau develops at 9 higher elds. Next, we shall focus on the thermal dependence of susceptibility times temperature (wt) product as shown in Fig. 4. Zero-eld curve displays an obvious manifestation of the quantum ferrimagnet; wt data exhibit upon cooling a round minimum followed by a steep low-temperature divergence. Since any non-zero eld opens an energy gap,