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Possible gapless chiral phase in a frustrated S = 1 1D antiferromagnet, CaV2O4

H. Kikuchi, M. Chiba, and T. Kubo

Abstract: We have measured magnetic susceptibility and 51V NMR of CaV2 O4 , a model substance for a frustrated S = 1 spin chain with competing rst- and second-neighbor anti-ferromagnetic interactions. Both the low-temperature magnetic susceptibility and the NMR Knight shift did not go down to zero as the temperature was lowered, suggesting that a spin gap is not present in CaV2 O4 . The absence of a spin gap gives us a clear contrast to the case of the nonfrustrated spin chains, which should have the Haldane gap. Recently published theoretical results for S = 1 XY or XXZ spin chain indicate that the gapless chiral phase could appear in a relatively broad region. Experimental results are discussed in terms of these theoretical predictions. A spin-freezing anomaly was observed at 20 K, reecting the spin-frustrating nature of the system. PACS Nos.: 75.30, 75.50 Rsum : Nous avons fait des mesures de susceptibilit et RMN sur le 51V dans le compos CaV2 O4 , une substance modle pour une chane de spin frustre S = 1 avec interactions rivales, plus proche voisin et antiferromagntique deuxime plus proche voisin. basse temprature, ni la susceptibilit, ni le dplacement RMN de Knight ne tendent vers zro avec la temprature, suggrant labsence dun intervalle (gap) de spin dans le CaV2 O4 . Labsence dun tel intervalle contraste avec le cas des chanes de spin non frustres qui devraient montrer un intervalle dHaldane. Des rsultats thoriques rcemment publis pour des chanes de spin XY ou XXZ, S = 1, montrent que la phase chirale sans intervalle pourrait exister sur une rgion assez vaste. Nous analysons les rsultats exprimentaux la lumire de ces prdictions thoriques. Une anomalie de gel de spin a t observe 20 K, retant la frustration de spin du systme. [Traduit par la Rdaction]

1. Introduction
The spin frustration system attracts much interest because of the variety in its phase diagram. The one-dimensional (1D) anti-ferromagnetic system with competing rst- (J1 ) and second-neighbor (J2 ) interactions, i.e., the zigzag system, is one of the most simple and intriguing systems with large quantum uctuations. The ground state of the zigzag system is altered dramatically by the presence of the second interaction. For example, in the case of S = 1/2, it has been pointed out theoretically that a phase

Received August 1, 2000. Accepted August 8, 2001. Published on the NRC Research Press Web site on November 29, 2001. H. Kikuchi1 and M. Chiba. Department of Applied Physics, Fukui University, Fukui 910-8507, Japan. T. Kubo. Department of Physics, Nara University of Education, Nara 630-8528, Japan.

Corresponding author .
DOI: 10.1139/cjp-79-11/12-1551 2001 NRC Canada

Can. J. Phys. 79: 15511555 (2001)


Can. J. Phys. Vol. 79, 2001

Fig. 1. (a) The crystal structure of CaV2 O4 . (b) The rst- and second-neighbor interactions J1 and J2 .

transition from the spin-liquid phase, without a spin gap, to the dimer phase, with a nite spin gap, will occur as an increasing ratio = J2 /J1 [1]. In the S = 1 one-dimensional system without secondneighbor interaction, it is well known that the Haldane gap is produced by the quantum effect. The effect of the frustrating second-neighbor interaction to the Haldane state is worthwhile investigating. Kolezhuk and his co-workers [2] calculated the change in the ground state caused by the second neighbor interaction in the S = 1 Heisenberg system and found a phase transition from the Haldane state to the spiral phase, although the spin gap remains nite in a whole range of . The existence of the gapless chiral phase in the XY model has been shown by exact diagonalization and DMRG (density matrix renormalization group) calculations [3]. DMRG calculations on the XXZ model [4] determined the phase diagram, and revealed that the gapless chiral phase exists in a broad region of the phase diagram. In the chiral phase, only the chirality exhibits long-range order, not accompanied by the conventional spin order. The chiral phase is a novel phase generated by both the quantum and frustration effects. It is a challenging task to observe and verify this topological phase experimentally. Searching model substances for the S = 1 anti-ferromagnetic zigzag chain, we found that tetragonal CaV2 O4 (with space group Pnma) approximates well to the model [5,6]. In CaV2 O4 , only V3+ (3d2 ) ions are magnetic, thus, spin number at each V3+ is expected to be S = 1. A primitive unit of the crystal structure is composed of double chains running parallel to the crystallographic b-axis (Fig. 1). In this material, adjacent V3+ ions with distance 3.01 in each chain are coupled through two oxygen ions (J2 ), and V3+ ions in different chains with distance 3.04 are also connected via two oxygen ions (J1 ), respectively. Since VOV bond lengths and bond angles for J1 and J2 are nearly identical, the value of J1 is expected to be almost same as that of J2 . We synthesized a polycrystalline sample of CaV2 O4 and measured the temperature dependence of the magnetic susceptibility (T ) and 51V NMR.
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Fig. 2. Temperature dependence of the magnetic susceptibility (T ) of a polycrystalline sample of CaV2 O4 in a magnetic eld of 100 Oe (full circle). (T ) imp (T ) is shown as open circles, where imp (T ) is the contribution by the magnetic impurities. The inset shows the low-temperature part of (T ) measured under eld-cooled (FC) and zero-eld-cooled (ZFC) conditions.

2. Experimental details
The polycrystalline sample of CaV2 O4 was synthesized from stoichiometric CaO, V2 O3+ and V. CaO was obtained from CaCO3 calcined at 1100 C for 24 h. V2 O3+ was made from V2 O5 , reduced under H2 gas atmosphere at 900 C. A small amount of V2 O3+ was oxidized to V2 O5 in air at 600 C and the mass change was measured to determine the oxygen content of V2 O3+ accurately . After mixing CaO, V2 O3+ and V in a dry box lled with argon gas, the mixed powder was calcined at 1100 C in a silica tube sealed in a vacuum. This process was repeated until a single-phase powder X-ray pattern was obtained. The magnetic susceptibility was measured using a Quantum Design SQUID magnetometer in the temperature range 5400 K. The 51V NMR spectra and the spin-lattice relaxation time were measured by a pulsed-spin-echo method in the temperature range from 1.5 K to room temperature. Electrical resistivity was measured using a standard four probe method.

3. Results
The resistivity increased exponentially with decreasing temperature with an activation energy of 1.4 103 K. Figure 2 indicates the temperature dependence of (T ) measured in a magnetic eld of 100 Oe. A broad maximum is observed around 250 K. The inset shows the low-temperature part of (T ). Zero-eld-cooled and eld-cooled magnetization differ from each other below Tf = 20K, suggesting the occurrence of spin-glass or spin-freezing transition. (T ) increased gradually below about 80 K as the temperature decreased. A single 51V NMR line without structure was observed at 1.5 K with an operating frequency of 46.5 MHz. The signal intensity weakened with increasing temperature and disappeared at about 160 K because of the sensitivity of the apparatus. The resonance eld did not depend on temperature. In Fig. 3, the Knight shift is plotted against temperature.
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Can. J. Phys. Vol. 79, 2001

Fig. 3. The temperature dependence of the Knight shift of 51V NMR line (full circle). The magnetic susceptibility (open circle) is shown for the comparison.

The temperature dependence of the spin-lattice relaxation rate T11 was measured in a eld between 3.99 and 8.85 T. T11 is approximately proportional to temperature.

4. Discussion
The broad maximum in (T ) at about 250 K shows characteristics of the 1D anti-ferromagnet, which implies a presence of dominant anti-ferromagnetic interactions. The spin glasslike anomaly occurred at 20 K strongly suggests the geometrical spin frustration effect. Similar magnetic anomalies, instead of conventional long-range order, are often observed in the geometrically frustrated magnets [7]. The origin of the frustration in our magnetic system is the presence of the competing rst- and secondneighbor interactions, which is inferred by consideration based on the crystal structure. Thus, CaV2 O4 is regarded as a good model substance for the S = 1 1D spin-frustrated anti-ferromagnet . The low-temperature magnetic susceptibility gives good information on the low-energy magnetic excitation, especially on the spin gap. However, since the low-temperature (T ) is often masked by the susceptibility of magnetic impurities imp (T ), we cannot determine from (T ) alone whether the origin of the observed upturn in the low-temperature (T ) is intrinsic or extrinsic. On the other hand, NMR has the advantage that it is insensitive to the presence of small amounts of magnetic impurities. Thus, we can separate an essential bulk spin contribution b (T ) from the total magnetic susceptibility by comparing (T ) and the Knight shift of the NMR line. The low-temperature (T ) as well as the Knight shift are indicated in Fig. 3. Both the (T ) and the Knight shift have almost similar temperature dependence above about 60 K. However, below this temperature, (T ) increases gradually with decreasing temperature, whereas the Knight shift remains almost constant. Supposing that the Knight shift is proportional to b (T ), the low-temperature part of (T ) is understood as a sum of b (T ) and imp (T ). We have estimated imp (T ) so that the temperature dependence of b (T ) is close to that of the Knight shift in the range of the experimental error. Assuming that imp (T ) follows the CurieWeiss law, that is imp (T ) = C/(T + ), we determined the Curie constant C = 0.02 emu (K/mol) and the Weiss temperature = 20 K. The concentration of the impurities are estimated to be about 2%, if the magnetic impurities are composed of V3+ ions. b (T ) = (T ) imp (T ) is shown in Fig. 2 in open circles. Above Tf , the intrinsic bulk susceptibility of CaV2 O4 is, hence, almost temperature independent in the low-temperature region. This low-temperature behavior of (T ) is completely different from that
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of the nonfrustrating S = 1 Heisenberg anti-ferromagnet in which (T ) drops exponentially toward zero as T 0 because of the nite spin gap (Haldane gap). Thus, in CaV2 O4 , we can conclude that the spin gap is zero or too small to observe under our experimental conditions. The temperature dependence of T1 cannot be understood in terms of thermal activation process, suggesting also the absence of the spin gap. As described in the introduction, the gapless chiral phase is expected theoretically for the frustrating S = 1 anti-ferromagnetic XY or XXZ model. It has been claimed that the gapless phase will appear, if XY-like magnetic anisotropy larger than a critical value is added to the frustrating and gapped Heisenberg chain [3, 4]. The ideal XY magnets are, however, scarcely found among actual materials. Instead, the single-ion anisotropy D is usually realized as the magnetic anisotropy for S 1. Recently, it has been shown that a positive single-ion anisotropy in the S = 1 frustrating 1D Heisenberg antiferromagnet tends to break the gapped ground state [8]. Since the sign of the D-term of the V3+ ion in an octahedral crystal eld is usually positive [9], it is very likely that the ground state of CaV2 O4 is gapless because of both the frustrating interaction and the positive D anisotropy. It is very interesting to compare our results with the theoretical magnetic phase diagram. However, because a single crystal of CaV2 O4 is not available now and a theoretical curve of the magnetic susceptibility is not calculated, we cannot determine values of the magnetic anisotropy and magnetic interactions. More experimental and theoretical studies are desired to clarify the magnetic properties of CaV2 O4 .

5. Summary
We have measured the magnetic susceptibility and 51V NMR of CaV2 O4 , and found this material to be a good model substance for a frustrated S = 1 spin chain with competing rst- and second-neighbor anti-ferromagnetic interactions. Both the low-temperature magnetic susceptibility and the NMR Knight shift suggest that a spin gap is not present in CaV2 O4 . We compared our experiments with theoretical studies, which predict the emergence of the gapless phase in S = 1 XY or XXZ spin chain, and pointed out the possibility of the realization of the gapless chiral phase.

We thank Professors T. Shinjo, N. Hosoito, and K. Mibu at the Institute for Chemical Research, Kyoto University for allowing us to use the SQUID magnetometer. We also thank Professor S.Yamamoto at Okayama University for his fruitful discussions.

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