Large negative thermal expansion in GdFe(CN)6 driven by unusual low-frequency modes

Gao, Qilong; Jiao, Yixin; Sanson, Andrea; Liang, Erjun; Sun, Qiang

doi:10.1016/j.cclet.2022.05.078

Cited by 14 publications

(3 citation statements)

References 42 publications

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“…Compared to other rigid NTE modes, these modes have larger negative Gruneisen parameters, indicating an important contribution to NTE. 32,33 This may explain why the NTE observed in hexagonal Ln(Co, Fe)(CN) 6 (Ln = La, Pr, Sm, Ho, Lu, Y) systems is much larger than in cubic A(Co, Fe)(CN) 6 (A = Ga, Fe, Ti, Sc). 34,35 Hence, the influence of nonrigid vibration modes on the NTE is also very important.…”

Section: Introductionmentioning

confidence: 99%

“…This modes are located at low frequencies where the LnN 6 trigonal prisms twist about their axes, causing the top and bottom triangular faces to rotate in opposite directions toward antiprismatic configurations, while the (Co, Fe)C 6 units rotate to accommodate this movement. Compared to other rigid NTE modes, these modes have larger negative Grüneisen parameters, indicating an important contribution to NTE. , This may explain why the NTE observed in hexagonal Ln(Co, Fe)(CN) 6 (Ln = La, Pr, Sm, Ho, Lu, Y) systems is much larger than in cubic A(Co, Fe)(CN) 6 (A = Ga, Fe, Ti, Sc). , Hence, the influence of nonrigid vibration modes on the NTE is also very important. Recently, some studies have begun to focus on the contribution of acoustic phonon modes to NTE.…”

Section: Introductionmentioning

confidence: 99%

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Critical Role of Nonrigid Unit and Spiral Acoustical Modes in Designing Colossal Negative Thermal Expansion

Gao,

Jiao,

Sprenger

et al. 2024

J. Am. Chem. Soc.

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Exploring the relationship between thermal expansion and structural complexity is a challenging topic in the study of modern materials where volume stability is required. This work reports a new family of negative thermal expansion (NTE) materials, AM(CN) 4 with A = Li and Na and M = B, Al, Ga, and In. Here, the compounds of LiB(CN) 4 and NaB(CN) 4 were only synthesized; others were purely computationally studied. A critical role of nonrigid vibrational modes and spiral acoustical modes has been identified in NaB(CN) 4 . This understanding has been exploited to design the colossal NTE materials of NaM(CN) 4 (M = Al, Ga, In). A joint study involving synchrotron X-ray diffraction, Raman spectroscopy, and first-principles calculations has been conducted to investigate the thermal expansion mechanism. It has been found that the A atoms can either increase the symmetry of the crystal structure, inducing stronger NTE, or lower the crystal symmetry, thus resulting in positive thermal expansion. Conversely, the M-site atoms do not affect the crystal structure. However, as the radius of the M atoms increases, the ionic nature of the C−M bonds strengthens and the CN vibrations become more flexible, thereby enhancing the NTE behavior. This study provides new insights to aid in the discovery and design of novel NTE materials and the control of thermal expansion.

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Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Critical Role of Nonrigid Unit and Spiral Acoustical Modes in Designing Colossal Negative Thermal Expansion

Gao,

Jiao,

Sprenger

et al. 2024

J. Am. Chem. Soc.

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“…The occurrence of NTE is mainly caused by low-frequency phonon vibration, ,, ferroelectric spontaneous polarization, magnetic transitions, − intermetallic charge transfer, , size effect, , and so on. The low-frequency phonon vibration mainly occurs in oxides, − ReO 3 -type fluorides, − organic open frameworks, , and Prussian blue analogues (PBAs). − These phonon-driven NTE materials generally exhibit a large temperature range of NTE …”

Section: Introductionmentioning

confidence: 99%

Influence of A/B Element Substitution on Negative Thermal Expansion in AB(CN)₆ (A = Al, Ga, In; B = Co, Fe, Mn, Cr, V, Ti): A Density Functional Theory Study

Jiao,

Liu,

Gao

et al. 2023

Inorg. Chem.

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Negative thermal expansion as an abnormal physical behavior of materials has promising applications in a high sophisticated equipment field, but the materials are rare. Here, we use the first-principles calculations based on density functional theory combined with the recently developed average atomic volume (AAV = V/N, where V is unit cell volume and N is the number of atoms in the unit) rule to predict the large isotropic negative thermal expansion materials of Prussian blue analogues AB(CN) 6 (A = Al, Ga, In; B = Co, Fe, Mn, Cr, V, Ti) in a wide temperature range. Our results clearly show that the coefficient of negative thermal expansion has a near-linear relationship with the average atomic volume of the systems and is also influenced by the element substitution at the A or B site. Lattice dynamic simulations indicate that the main contribution to the negative thermal expansion comes from the low-frequency transverse vibration of the (B)−C�N−(A) groups, especially the transverse vibration of the N atoms. Thus, the element substitution at the A site (binding to N) can tune the negative thermal expansion behavior of the systems more effectively than that at the B site (binding to C), indicating the different roles of bonds on the negative thermal expansion. Our present work not only expands the kinds of isotropic materials but also gives some insights into the relationship between the average atomic volume and negative thermal expansion.

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A new isotropic negative thermal expansion material of CaSnF6 with facile and low-cost synthesis

et al. 2022

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Large negative thermal expansion in GdFe(CN)6 driven by unusual low-frequency modes

Cited by 14 publications

References 42 publications

Critical Role of Nonrigid Unit and Spiral Acoustical Modes in Designing Colossal Negative Thermal Expansion

Critical Role of Nonrigid Unit and Spiral Acoustical Modes in Designing Colossal Negative Thermal Expansion

Influence of A/B Element Substitution on Negative Thermal Expansion in AB(CN)₆ (A = Al, Ga, In; B = Co, Fe, Mn, Cr, V, Ti): A Density Functional Theory Study

A new isotropic negative thermal expansion material of CaSnF6 with facile and low-cost synthesis

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Large negative thermal expansion in GdFe(CN)6 driven by unusual low-frequency modes

Cited by 14 publications

References 42 publications

Critical Role of Nonrigid Unit and Spiral Acoustical Modes in Designing Colossal Negative Thermal Expansion

Critical Role of Nonrigid Unit and Spiral Acoustical Modes in Designing Colossal Negative Thermal Expansion

Influence of A/B Element Substitution on Negative Thermal Expansion in AB(CN)6 (A = Al, Ga, In; B = Co, Fe, Mn, Cr, V, Ti): A Density Functional Theory Study

A new isotropic negative thermal expansion material of CaSnF6 with facile and low-cost synthesis

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Product

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Influence of A/B Element Substitution on Negative Thermal Expansion in AB(CN)₆ (A = Al, Ga, In; B = Co, Fe, Mn, Cr, V, Ti): A Density Functional Theory Study