NMR, magnetization, and heat capacity studies of the uniform spin-
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 chain compound 
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Chakrabarty, Tanmoy; Heinmaa, Ivo; Verchenko, Valeriy Yu.; Paulose, P. L.; Stern, Raivo

doi:10.1103/physrevb.100.094431

Cited by 7 publications

(3 citation statements)

References 63 publications

(111 reference statements)

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“…Further, the magnetization data at T = 2 K were fitted well using the phenomenological expression for a spin chain, M chain = αH + β √ H . The obtained parameters α 5.46 × 10 −7 and β 5.02 × 10 −5 are comparable with the values reported for the spin- 1 2 chain compound Bi 6 V 3 O 16 [49].…”

Section: B Magnetizationsupporting

confidence: 87%

Quasi-one-dimensional uniform spin- 12 Heisenberg antiferromagnet KNaCuP2O7 probed by
Guchhait
¹
,
Ding
²
,
Sahoo
³

et al. 2021
Phys. Rev. B

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We present the structural and magnetic properties of KNaCuP 2 O 7 investigated via x-ray diffraction, magnetization, specific heat, and 31 P and 23 Na NMR measurements and complementary electronic structure calculations. The temperature-dependent magnetic susceptibility and 31 P NMR shift could be modeled very well by the uniform spin-1 2 Heisenberg antiferromagnetic chain model with a nearest-neighbor interaction J/k B 58.7 K. The corresponding mapping using first-principles electronic structure calculations leads to J DFT /k B 59 K with negligibly small interchain couplings, further confirming that the system is indeed a one-dimensional uniform spin-1 2 Heisenberg antiferromagnet. The diverging trend of NMR spin-lattice relaxation rates ( 31 1/T 1 and 23 1/T 1 ) implies the onset of a magnetic long-range ordering at around T N 1 K. From the value of T N , the average interchain coupling is estimated to be J /k B 0.28 K. Moreover, the NMR spin-lattice relaxation rates show the dominant contributions from uniform (q = 0) and staggered (q = ±π/a) spin fluctuations in the high-and low-temperature regimes, respectively, mimicking one-dimensionality of the spin lattice. We have also demonstrated that 31 1/T 1 in high temperatures varies linearly with 1/ √ H , reflecting the effect of spin diffusion on the dynamic susceptibility. The temperature-dependent unit cell volume could be described well using the Debye approximation with a Debye temperature of D 294 K, consistent with the heat capacity data.

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Section: B Magnetizationsupporting

confidence: 87%

Quasi-one-dimensional uniform spin- 12 Heisenberg antiferromagnet KNaCuP2O7 probed by
Guchhait
¹
,
Ding
²
,
Sahoo
³

et al. 2021
Phys. Rev. B

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“…This is because, our maximum measured field of 9 T is far below the expected saturation field H s = 2J/gµ B 78.5 T, taking J/k B 55.5 K [21]. Further, the magnetization data at T = 2 K were fitted well using the phenomenological expression for a spin chain, M chain = αH + β √ H. The obtained parameters α 5.46×10 −7 and β 5.02×10 −5 are comparable with the values reported for spin-1/2 chain compound Bi 6 V 3 O 16 [48].…”

Section: B Magnetizationsupporting

confidence: 63%

Quasi-one-dimensional uniform spin-$\frac{1}{2}$ Heisenberg antiferromagnet KNaCuP$_2$O$_7$ probed by $^{31}$P and $^{23}$Na NMR

Guchhait,

Ding,

Sahoo

et al. 2021

Preprint

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We present the structural and magnetic properties of KNaCuP2O7 investigated via x-ray diffraction, magnetization, specific heat, and 31 P NMR and 23 Na NMR measurements and complementary electronic structure calculations. The temperature dependent magnetic susceptibility and 31 P NMR shift could be modeled very well by the uniform spin-1/2 Heisenberg antiferromagnetic chain model with nearest-neighbour interaction J/kB 58.7 K. The corresponding mapping using first principles electronic structure calculations leads to J DFT /kB 59 K with negligibly small inter-chain couplings (J /kB, J /kB < 0.1 K), further confirming that the system is indeed an one-dimensional uniform spin-1/2 Heisenberg antiferromagnet. The temperature-dependent unit cell volume could be described well using the Debye approximation with a Debye temperature of ΘD 294 K, consistent with the heat capacity data. The diverging trend of the NMR spin-lattice relaxation rates ( 31 1/T1 and 23 1/T1) imply the onset of a magnetic long-range-ordering at very low temperatures supporting the anticipated TN 0.38 K from the inter-chain couplings. Moreover, the NMR spin-lattice relaxation rates show the dominant contributions from uniform (q = 0) and staggered (q = ±π/a) spin fluctuations in the high and low temperature regimes, respectively mimicking one-dimensionality of the spin-lattice. We have also demonstrated that 31 1/T1 in high temperatures varies linearly with 1/ √ H reflecting the effect of spin diffusion on the dynamic susceptibility. Further, the interchain frustration also substantially impede the magnetic ordering rendering the spin-lattice a perfect one-dimensional uniform spin-1/2 Heisenberg antiferromagnet over a wide temperature range.

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“…The low-temperature increase in susceptibilities observed at 50 and 25 K in RbV 3 O 8 , and TlV 3 O 8 , respectively, is most likely a result of isolated spins. 54 , 55 Alternatively, the feature could possibly arise from ferromagnetic exchange coupling between canted-spin V n + centers. 56 The observed differences in the magnetic transition temperatures with the different cations can be attributed to differences in V···V bond distances, which ultimately reflect distortions of local structure resulting from the presence of the 6s 2 lone-pair in Tl + cations.…”

Section: Resultsmentioning

confidence: 99%

Effect of Stereochemically Active Electron Lone Pairs on Magnetic Ordering in Trivanadates

Agbeworvi,

Zaheer,

Ponis

et al. 2023

Inorg. Chem.

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Stereoactive electron lone pairs derived from filled 5/6s 2 states of p-block cations are an intriguing electronic and geometric structure motif that have been exploited for diverse applications such as thermoelectrics, thermochromics, photocatalysis, and nonlinear optics. Layered trivanadates are dynamic intercalation hosts, where the insertion of cations can be used to tune electron correlation, charge localization, and magnetic ordering. However, the interaction of 5/6s 2 stereoactive electron lone pairs with layered trivanadates remains unexplored. In this study, we contrast s-and p-block trivanadates and map off-centering in the coordination environment and reduction in symmetry arising from the stereochemical activity of lone pair cations to the emergence of filled antibonding lone-pair 6s 2 −O 2p hybridized states. The former is studied by high-resolution single-crystal X-ray diffraction studies of TlV 3 O 8 and isostructural RbV 3 O 8 to probe distinct differences in Tl and Rb coordination environments and the resulting modulation of V−V interactions in V 3 O 8 slabs. The latter has been probed by variable-energy hard X-ray photoelectron spectroscopy (HAXPES) measurements, which manifest orbital-specific contributions from bonding and antibonding interactions of stereoactive Tl 6s 2 electron lone pairs in TlV 3 O 8 . The spectroscopic assignment of valence band states to stereoactive lone pairs is further corroborated by first-principles electronic structure calculations, crystal orbital Hamilton population analyses, and electron localization function maps. The presence of the Tl 6s 2 electron lone pair in TlV 3 O 8 brings about the off-centering of Tl + cations, which leads to anisotropy in Tl−O bonds. The off-centering of Tl ions weakens V−O bonds in one direction, which subsequently strengthens directional V−V coupling. Magnetic measurements reveal ferromagnetic signatures for both RbV 3 O 8 and TlV 3 O 8 . However, the differences in V•••V interactions significantly affect the energy balance of the superexchange interactions, resulting in an ordering temperature of 140 K for TlV 3 O 8 as compared to 125 K for RbV 3 O 8 . The results demonstrate the distinctive effects of stereochemically active lone pairs in modifying electronic structure near the Fermi level and for mediating superexchange interactions.

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NMR, magnetization, and heat capacity studies of the uniform spin- 12 chain compound Bi6V3O16

Cited by 7 publications

References 63 publications

Quasi-one-dimensional uniform spin- 12 Heisenberg antiferromagnet KNaCuP2O7 probed by
Guchhait
¹
,
Ding
²
,
Sahoo
³

et al. 2021
Phys. Rev. B

Quasi-one-dimensional uniform spin- 12 Heisenberg antiferromagnet KNaCuP2O7 probed by
Guchhait
¹
,
Ding
²
,
Sahoo
³

et al. 2021
Phys. Rev. B

Quasi-one-dimensional uniform spin-$\frac{1}{2}$ Heisenberg antiferromagnet KNaCuP$_2$O$_7$ probed by $^{31}$P and $^{23}$Na NMR

Effect of Stereochemically Active Electron Lone Pairs on Magnetic Ordering in Trivanadates

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NMR, magnetization, and heat capacity studies of the uniform spin- 12 chain compound Bi6V3O16

Cited by 7 publications

References 63 publications

Quasi-one-dimensional uniform spin- 12 Heisenberg antiferromagnet KNaCuP2O7 probed by Guchhait1, Ding2, Sahoo3 et al. 2021Phys. Rev. B

Quasi-one-dimensional uniform spin- 12 Heisenberg antiferromagnet KNaCuP2O7 probed by Guchhait1, Ding2, Sahoo3 et al. 2021Phys. Rev. B

Quasi-one-dimensional uniform spin-$\frac{1}{2}$ Heisenberg antiferromagnet KNaCuP$_2$O$_7$ probed by $^{31}$P and $^{23}$Na NMR

Effect of Stereochemically Active Electron Lone Pairs on Magnetic Ordering in Trivanadates

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Product

Resources

About

Quasi-one-dimensional uniform spin- 12 Heisenberg antiferromagnet KNaCuP2O7 probed by
Guchhait
¹
,
Ding
²
,
Sahoo
³

et al. 2021
Phys. Rev. B

Quasi-one-dimensional uniform spin- 12 Heisenberg antiferromagnet KNaCuP2O7 probed by
Guchhait
¹
,
Ding
²
,
Sahoo
³

et al. 2021
Phys. Rev. B