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  • 1
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 69 (1991), S. 5807-5809 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Recent magnetic susceptibility measurements on polycrystalline MnCl2⋅H2O indicate that it behaves like a quasi-one-dimensional antiferromagnet. The heat capacity of this compound has now been measured between ∼0.5 and 80 K in a liquid-3He-cooled vacuum calorimeter. Cp exhibits a large, sharp λ-type peak at TN = 2.18 ± 0.01 K marking the onset of long-range spin order. The critical entropy S(TN) is found to be ∼0.40R ln 6, confirming the short-range, low-dimensional nature of most of the spin ordering. An anisotropic elastic continuum model has been used to calculate the contribution of lattice vibrations to Cp. The data above ∼3 K are well represented by this model (with suitable choice of three parameters) plus the theoretical heat capacity of the 1D Heisenberg antiferromagnet with S =5/2 and exchange constant J/k=−0.45 K. Below ∼ 0.7TN, the magnetic part of Cp is well described by an anisotropic 3D spin-wave model with Jz/k = J/k = −0.45 K, Jx/k = Jy/k = −0.015 K, and an anisotropy field HA ≈ 3.3 kOe. The intra- and interchain exchange constants agree well with those inferred from χM. 〈lz〉
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  • 2
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 73 (1993), S. 5386-5388 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: The magnetic behavior of Ni(SCN)2 has been studied at low temperatures for the first time. A Curie–Weiss fit, χM=C/(T−θ), to the susceptibility between 100 and 300 K yields g=2.13±0.01 (S=1) and θ=39.8±1.4 K. Systematic curvature in χ−1 vs T is evident, however. Despite the large positive θ Ni(SCN)2 appears to order antiferromagnetically at Tc=52±1 K, slightly below a maximum in χ(T) at T(χmax)=57.2±0.5 K, with χmax=0.0331±0.0003 emu/mol. The ratio Tc/T(χmax)=0.91±0.02 does not suggest lower magnetic dimensionality. Magnetization isotherms are linear to 16 kG; some features suggesting lower temperature transitions occur. Well above Tc the susceptibility is analyzed assuming axial and rhombic crystal field distortions, i.e., D[Sˆz2−S(S+1)/3] and E[Sˆx2−Sˆy2] spin Hamiltonian terms, with exchange incorporated in a mean field approximation. An extraordinarily large ||D/k||≈119 K seems to emerge, a result which is very provisional lacking single crystal data. A mean field analysis of Tc and θ yields ferromagnetic intrachain exchange J1/k=8.6±0.5 K and antiferromagnetic interchain exchange J2/k=−0.76±0.4 K. It seems more likely that D is negative, but even if it is positive the exchange interaction is large enough to induce magnetic order at finite Tc in light of theories relating Tc, J, and D.
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  • 3
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 73 (1993), S. 5654-5656 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Recent studies of the magnetic susceptibility of powdered Fe[S2CNC4H8]2I confirm that Fe(III) in this salt is in the unusual spin state S=3/2 and that the system behaves as a quasi-2D antiferromagnet. Analysis of the data indicates that the ||±1/2(approximately-greater-than) ground doublet is separated by Δ/k=18.7 K from an excited ||±3/2(approximately-greater-than) doublet. We have now measured the heat capacity of polycrystalline Fe[S2CNC4H8]2I between 0.5 and 80 K in a liquid 3He-cooled calorimeter. CP exhibits a λ-type peak at TN=2.18±0.01 K. The critical entropy, S(TN)=0.25R ln2, indicates that most of the spin order is of a short-range, low-dimensional nature. The contribution of lattice vibrations to CP was estimated using the method of Sorai and Seki [J. Phys. Soc. Jpn. 32, 382 (1972)], which assumes a Schottky contribution from two doublets whose separation Δ was determined from the magnetic data. At the same time, the cooperative peak was reasonably represented by the results for the 2D S=1/2 XY model with Jxy/k=−2.18 K. In order to obtain a self-consistent fit of the lattice heat capacity, however, it was necessary to use a larger splitting (Δ/k=32 K) than that found from susceptibility data. This discrepancy between the doublet-doublet separations indicated by χ and CP measurements may suggest a possible temperature dependence of Δ.
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  • 4
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 69 (1991), S. 6004-6006 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: The magnetic properties of Ni(SCN)2(C2H5OH)2 have been studied, the first Ni(II) system in the general family of compounds M(SCN)2(ROH)2 (where M=divalent Mn, Fe, Co, or Ni and R=CH3, C2H5, i- or n-C3H7) to be examined at low temperatures. In contrast to previously studied Mn(II) and Co(II) members of this family, which exhibit predominant antiferromagnetism, the present compound is ferromagnetic. The susceptibility of a polycrystalline sample is of Curie–Weiss form only above 75 K, with g¯ = 2.175 ± 0.01 and S=1 and with θ=24.1±1.0 K. The initial susceptibility is well accounted for by an asymptotic critical law, χ0 = Γ[T/Tc − 1]−γ, in the reduced temperature range 0.147–0.013, with Tc = 13.081 ± 0.01 K, γ=1.354±0.02, and Γ=0.0925±0.003 emu/mol. The γ value is between 3D-XY and 3D-Heisenberg model predictions. The susceptibility in the paramagnetic regime well above Tc is analyzed including the effects of axial and rhombic crystal field distortions, represented by D[Sˆ2z − S(S + 1)/3] and E[Sˆ2x − Sˆ2y] terms in the spin Hamiltonian, and incorporating exchange interactions in a mean-field approximation. An excellent fit is obtained with g=2.175, D/k=−64.3±5 K, E/k=23.1±4 K, and zJ/k=19.4±1 K. The magnitude of D is the largest we know of in a Ni(II) compound. The three spin states of the 3A crystal field ground term are strongly split, probably contributing to the relatively low value of Tc compared to zJ/k. Some two-dimensional character in the exchange, as has been found for other members of this family of compounds, may also contribute.
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  • 5
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: The magnetic properties of Fe[S2CNC4H8]2I have been studied, the first pentacoordinate Fe(III) system of this type with a cyclic terminal group, rather than an alkyl group, to be examined in detail. The susceptibility of a polycrystalline sample is of Curie–Weiss form above 30 K, with g¯=2.16 ±0.02 and S=3/2 and with θ=−0.75±1.0 K. Thus the unusual intermediate spin state occurs here as in earlier examples. The susceptibility can be fit quite well down to about 6 K assuming that axial and rhombic crystal field distortions occur, represented by D[Sˆ2z − S(S + 1)/3] and E[Sˆ2x − Sˆ2y] terms in the spin Hamiltonian, and incorporating exchange interactions in a mean-field approximation. Fitted parameters are D/k=9.3± 0.5 K, E/k=−0.6±0.2 K, gx=2.23± 0.05, gy= 2.19 ± 0.05, gz=2.04 ± 0.05, and zJ/k=−0.235 ±0.02 K. At low temperatures the susceptibility exhibits a broad maximum with T(χmax)=3.23± 0.04 K and χmax =0.376±0.004 emu/mol. An antiferromagnetic transition at Tc=2.21±0.01 K is inferred from the position of a maximum in (∂χ/∂T), an ordering temperature in reasonable agreement with earlier Mössbauer results. The ratio Tc/T(χmax) =0.68±0.01 is suggestive of quasi-two-dimensionality. In the region of the maximum an acceptable fit according to a 2D- XY model with plausible parameter values can be achieved, but only with a ferromagnetic interlayer exchange interaction about 28% as strong as the leading antiferromagnetic intralayer interaction. Isotherms of M vs H show somewhat unusual curvature, the explanation of which is unclear.
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  • 6
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 73 (1993), S. 5503-5503 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Previous magnetization and susceptibility measurements on the mixed magnet Co1−xMnxCl2⋅2H2O disclosed a spin glass transition near 2.45 K over a wide composition range.1 Recent heat capacity and NMR measurements have confirmed and extended this finding.2 The time dependence of the thermoremanent magnetization (TRM) below Tg for an x=0.452 mixture was studied in some detail1 and was found to conform approximately to a decay of stretched exponential type, or perhaps slightly more accurately to the product of a stretched exponential and a power law. Small systematic deviations of data from fitted curves were apparent however. Recently a percolation model for relaxation in random systems was proposed,3 and yielded significantly improved fits to the TRM decay in an Au:Fe spin glass. The model assumes dispersive excitations within fixed finite domains, and includes as parameters the fastest and slowest relaxation rates characterizing the spectrum of domains. We find that this model also permits much better fits to be obtained for the TRM decay in Co1−xMnxCl2⋅2H2O, x=0.452. Systematic deviations that were present when using more traditional decay functions are virtually eliminated. The variation of fitted parameters with cooling field and temperature is also explored.
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  • 7
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 85 (1999), S. 4527-4529 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Reported here are field-cooled (FC) and zero-field-cooled (ZFC) magnetizations (MFC and MZFC, respectively) in smaller and larger fields than used in previous work, and thermoremanent magnetization data (TRM) for various temperatures and wait times. For fields of 12.8 and 0.1 G a separation between MFC and MZFC develops near 9 K, well below the 16.1 K magnetization maximum or the ∼14 K antiferromagnetic transition; thus, reentrant behavior occurs as for the higher fields used previously. Maxima in MZFC(T) are observed at 7.2 and 8.0 K for 12.8 and 0.1 G, respectively. Similar measurements in fields of from 3.0 to 15.5 kG show an evolution in the form of MFC(T) and MZFC(T); the separation between these develops at somewhat higher temperatures than 9 K and no maximum appears in MZFC. The field dependence of (MIRR/H)MAX, where MIRR=MFC−MZFC, is determined and shows a change in regime between 2 and 3 kG. The TRM as a function of time is measured for temperatures of 1.6, 4.3, and 5.8 K, with wait times ranging from 10 to 500 min. The relaxation rate is quite small, consistent with glassy dynamics with a wide distribution of relaxation times, and increases with increasing temperature. Remarkably, however, aging effects are absent even at 5.8 K, although this is 69% of the splitting temperature between MFC and MZFC. An explanation may reside in randomized antiferromagnetic couplings between chemical chains which are individually ordered ferromagnetically, and in the formation of a structure of almost independent clusters. © 1999 American Institute of Physics.
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  • 8
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 87 (2000), S. 6540-6542 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: The title system is the first mixed insulating magnet to be examined composed of three separate magnetic components. Each of the three possible binary mixtures based on the same isostructural MCl2⋅2H2O components has been examined. The Co/Fe mixture has competing orthogonal spin anisotropies, the Co/Mn mixture competing ferromagnetic and antiferromagnetic exchange interactions, and the Fe/Mn mixture both competing anisotropies and competing exchange interactions. Hence various pairwise competitions will occur in a ternary mixture of these components. Four different compositions are examined, with (x,y)=(0.830,0.681), (0.623,0.464), (0.539,0.377), and (0.366,0.272). These provide representative coverage of several interesting regions in the three binary T−x phase diagrams, specifically in terms of a relative binary composition (rbc) which can be defined for a ternary mixture in pairwise fashion. High temperature susceptibilities follow a Curie–Weiss form χM=C/(T−θ) rather well. Curie constants are approximately as expected based on fractions of different metal ions present, and both C and θ are closest to values characterizing the Co/Mn binary mixture. Low temperature susceptibilities exhibit features suggesting phase transitions. The temperatures at which these occur are often close to what might be anticipated from the binary T−x phase diagrams for the appropriate rbc. In certain cases, however, transitions anticipated on such a basis do not seem to be present. The ternary mixtures also exhibit behavior suggestive of spin glass properties. © 2000 American Institute of Physics.
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  • 9
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 75 (1994), S. 5529-5531 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: Recent magnetic studies of polycrystalline CoCl2⋅H2O showed an antiferromagnetic ordering transition at TN∼14 K and an apparent spin glass transition at ∼7 K. We now have extended the magnetic susceptibility measurements up to 300 K. The results above TN can be well described if the lowest electronic states of Co2+ in this salt are two Kramers doublets separated by ΔE/k=230 K, and if a predominantly ferromagnetic mean field interaction is introduced. The heat capacity of CoCl2⋅H2O over the range 0.6–80 K has also been measured. Below ∼10 K, Cp≈aT−2+bT3. The first term is the hyperfine contribution of the 59Co2+ nuclei. The second is the sum of lattice vibrational and electronic spin parts. Cp exhibits a λ-type peak at TN1=15.0±0.05 K, and a second λ anomaly of comparable size at TN2=13.9±0.05 K, which appears to be associated with a spin reorientation transition. Correcting the observed Cp data for the nuclear spin contribution, one may calculate the sum of lattice vibration and electron spin entropies, and thus obtain at TN1 an upper limit to the critical magnetic entropy. This amounts to 0.38 R ln 2, suggesting that a substantial part of the spin ordering in this system is of short-range and lower dimensionality. Cp also exhibits an inflection point near 4.5 K, where an unusual feature in the temperature dependence of the spin glass thermoremanent magnetization was found.
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  • 10
    Electronic Resource
    Electronic Resource
    [S.l.] : American Institute of Physics (AIP)
    Journal of Applied Physics 79 (1996), S. 4718-4720 
    ISSN: 1089-7550
    Source: AIP Digital Archive
    Topics: Physics
    Notes: The trihydrate of nickelous bromide, NiBr2⋅3H2O, is examined magnetically for the first time. A Curie–Weiss fit, χM=C/(T−θ), to the susceptibility between 70 and 300 K yields g=2.31±0.01 (S=1) and θ=6.6±0.5 K. Systematic curvature in χ−1 vs T is evident below 70 K. Despite the positive θ, NiBr2⋅3H2O appears to order antiferromagnetically at Tc=3.82±0.05 K, somewhat below a maximum in χ(T) at T(χmax)=6.17±0.10 K, with χmax=0.0900±0.0005 emu/mol. The ratio Tc/T(χmax)=0.62±0.01 suggests lower magnetic dimensionality. Between 4 and 12 K an acceptable fit with a two-dimensional Heisenberg model can be made, with g=2.58±0.01, J/k=−1.36±0.02 K (assuming Hˆex=−2J∑i(approximately-greater-than)jSˆi⋅Sˆj), and a correction for interlayer exchange z′J′/k=−0.99±0.02 K. Well above Tc the susceptibility is analyzed assuming axial and rhombic crystal field distortions, i.e., D[Sˆ2z−S(S+1)/3] and E[Sˆ2x−Sˆ2y] spin Hamiltonian terms, with exchange included in a mean field approximation: g=2.33±0.02, D/k=57.3±5.0 K, E/k=−24.9±3.0 K, and zJ/k=5.28±0.20 K. The parameters are provisional lacking single-crystal data, but the zero-field splitting is clearly quite large. Magnetization versus field isotherms depart only slightly from linearity for fields above 10 kG, and show a small hysteresis, even for temperatures above Tc. It is likely that ferromagnetically coupled NiBr2NiBr2Ni... chains are present, and that there are antiferromagnetic interactions between chains, such that strongly coupled layers occur, with weaker interactions between layers. © 1996 American Institute of Physics.
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