Exploring new abnormal thermal expansion materials is important to understand the nature of thermal expansion.Metal-organic framework(MOF)with unique structure flexibility is an ideal material to study the thermal exp...Exploring new abnormal thermal expansion materials is important to understand the nature of thermal expansion.Metal-organic framework(MOF)with unique structure flexibility is an ideal material to study the thermal expansion.This work adopts the high-resolution variable-temperature powder x-ray diffraction to investigate the structure and intrinsic thermal expansion in Sr-MOF([Sr(DMPhH_(2)IDC)_(2)]_n).It has the unique honeycomb structure with one-dimensional(1 D)channels along the c-axis direction,the a-b plane displays layer structure.The thermal expansion behavior has strong relationship with the structure,ZTE appears in the a-b plane and large PTE along the c-axis direction.The possible mechanism is that the a/b layers have enough space for the transverse thermal vibration of polydentate ligands,while along the c-axis direction is not.This work not only reports one interesting zero thermal expansion material,but also provides new understanding for thermal expansion mechanism from the perspective of the structural model.展开更多
Double ReO_(3)-type fluorides have a great interest in the field of negative thermal expansion(NTE)and luminescent materials.However,their application is limited by the scarcity of quantity,expensive raw materials,and...Double ReO_(3)-type fluorides have a great interest in the field of negative thermal expansion(NTE)and luminescent materials.However,their application is limited by the scarcity of quantity,expensive raw materials,and harsh preparation conditions.In this work we have found a new NTE material,CaSnF_(6),by applying the concept of the average atomic volume.More importantly,different from the previous solid-phase sintering and direct fluorination methods,the nano CaSnF6 has been synthesized for the first time by solvothermal method.The results of X-ray diffraction(XRD)and Raman spectroscopy show that a phase transition occurs from rhombohedral(R3)to cubic(Fm3m)structure at about 200 K,and a strong isotropic NTE(αv=−15.78×10^(−6)K^(−1))appears in the cubic phase.Lattice dynamics calculations from first-principles illustrate that the NTE is due to the transverse vibration of fluorine atoms excited by low-frequency phonons.This work not only broadens the NTE family of fluorides,but also provides a new facile and low-cost fabricati on method for the preparation of NTE fluorides.展开更多
Understanding the negative thermal expansion(NTE)mechanism remains an important and challenging thing.In this work,we selected the case of YFe(CN)_(6)to investigate the structure-mechanism relation on the base of crys...Understanding the negative thermal expansion(NTE)mechanism remains an important and challenging thing.In this work,we selected the case of YFe(CN)_(6)to investigate the structure-mechanism relation on the base of crystal structure,electro nic structure and lattice dynamics.We expanded the NTE of YFe(CN)_(6)to 150 K,and the temperature dependence of volume and lattice constants was determined by temperature-variable synchrotro n X-ray diffraction measure ments.A large NTE was found in the system.Our theoretical calculations indicate that the Y-N bond exhibits a strong ionic feature through the calculated electron localization function(ELF),which has a strong influence on the anisotropic vibration of the N atom.The detailed lattice dynamics simulations suggest that the NTE of YFe(CN)_(6)may be related to the presence of the unusual low-frequency modes of the YN_(6)triangular prism(tri-prism)units.The optical branches with low frequencies are mainly related to the distortion and twisting modes of the YN_(6)tri-prism units,which contribute most to the NTE effect in the crystal.展开更多
Understanding the negative thermal expansion(NTE)mechanism is of great importance.In this work,we consider the new NTE compound Gd Fe(CN)_(6)(α_(v)=-34.2×10^(-6)K^(-1))as a case study to investigate the NTE mech...Understanding the negative thermal expansion(NTE)mechanism is of great importance.In this work,we consider the new NTE compound Gd Fe(CN)_(6)(α_(v)=-34.2×10^(-6)K^(-1))as a case study to investigate the NTE mechanism from the perspective of the lattice vibrational dynamics.The atomic mean-square displacements suggest that the NTE of Gd Fe(CN)_(6)comes from the strong tension effect induced by the transverse vibrations of the atomic-Fe-C≡N-Gd-linkages,with the largest contribution given by N atoms.Lattice dynamics calculations show that three low-frequency optical modes at about 50 cm^(-1)show the largest negative Grüneisen parameters thus providing the largest contribution to the NTE.The existence of these unusual low-frequency vibrational modes can be ascribed to the presence of GdN_(6)trigonal prisms in the framework structure of Gd Fe(CN)_(6).展开更多
基金Project supported by the National Natural Science Foundation of China(Grant Nos.22071221 and 21905252)the Natural Science Foundation of Henan Province,China(Grant No.212300410086)。
文摘Exploring new abnormal thermal expansion materials is important to understand the nature of thermal expansion.Metal-organic framework(MOF)with unique structure flexibility is an ideal material to study the thermal expansion.This work adopts the high-resolution variable-temperature powder x-ray diffraction to investigate the structure and intrinsic thermal expansion in Sr-MOF([Sr(DMPhH_(2)IDC)_(2)]_n).It has the unique honeycomb structure with one-dimensional(1 D)channels along the c-axis direction,the a-b plane displays layer structure.The thermal expansion behavior has strong relationship with the structure,ZTE appears in the a-b plane and large PTE along the c-axis direction.The possible mechanism is that the a/b layers have enough space for the transverse thermal vibration of polydentate ligands,while along the c-axis direction is not.This work not only reports one interesting zero thermal expansion material,but also provides new understanding for thermal expansion mechanism from the perspective of the structural model.
基金supported by the National Natural Science Foundation of China(Nos.22071221 and 21905252)Natural Science Foundation of Henan Province(Nos.212300410086,222301420040 and 222300420325).
文摘Double ReO_(3)-type fluorides have a great interest in the field of negative thermal expansion(NTE)and luminescent materials.However,their application is limited by the scarcity of quantity,expensive raw materials,and harsh preparation conditions.In this work we have found a new NTE material,CaSnF_(6),by applying the concept of the average atomic volume.More importantly,different from the previous solid-phase sintering and direct fluorination methods,the nano CaSnF6 has been synthesized for the first time by solvothermal method.The results of X-ray diffraction(XRD)and Raman spectroscopy show that a phase transition occurs from rhombohedral(R3)to cubic(Fm3m)structure at about 200 K,and a strong isotropic NTE(αv=−15.78×10^(−6)K^(−1))appears in the cubic phase.Lattice dynamics calculations from first-principles illustrate that the NTE is due to the transverse vibration of fluorine atoms excited by low-frequency phonons.This work not only broadens the NTE family of fluorides,but also provides a new facile and low-cost fabricati on method for the preparation of NTE fluorides.
基金supported by the National Natural Science Foundation of China(22071221,21905252)Natural Science Foundation of Henan Province(212300410086)。
文摘Understanding the negative thermal expansion(NTE)mechanism remains an important and challenging thing.In this work,we selected the case of YFe(CN)_(6)to investigate the structure-mechanism relation on the base of crystal structure,electro nic structure and lattice dynamics.We expanded the NTE of YFe(CN)_(6)to 150 K,and the temperature dependence of volume and lattice constants was determined by temperature-variable synchrotro n X-ray diffraction measure ments.A large NTE was found in the system.Our theoretical calculations indicate that the Y-N bond exhibits a strong ionic feature through the calculated electron localization function(ELF),which has a strong influence on the anisotropic vibration of the N atom.The detailed lattice dynamics simulations suggest that the NTE of YFe(CN)_(6)may be related to the presence of the unusual low-frequency modes of the YN_(6)triangular prism(tri-prism)units.The optical branches with low frequencies are mainly related to the distortion and twisting modes of the YN_(6)tri-prism units,which contribute most to the NTE effect in the crystal.
基金supported by the National Natural Science Foundation of China(Nos.22071221 and 21905252)the Natural Science Foundation of Henan Province(No.212300410086)Use of the Advanced Photon Source,an Office of Science User Facility operated for the U.S.Department of Energy(DOE)Office of Science by Argonne National Laboratory,was supported by the U.S.DOE under Contract No.DE-AC02-06CH11357。
文摘Understanding the negative thermal expansion(NTE)mechanism is of great importance.In this work,we consider the new NTE compound Gd Fe(CN)_(6)(α_(v)=-34.2×10^(-6)K^(-1))as a case study to investigate the NTE mechanism from the perspective of the lattice vibrational dynamics.The atomic mean-square displacements suggest that the NTE of Gd Fe(CN)_(6)comes from the strong tension effect induced by the transverse vibrations of the atomic-Fe-C≡N-Gd-linkages,with the largest contribution given by N atoms.Lattice dynamics calculations show that three low-frequency optical modes at about 50 cm^(-1)show the largest negative Grüneisen parameters thus providing the largest contribution to the NTE.The existence of these unusual low-frequency vibrational modes can be ascribed to the presence of GdN_(6)trigonal prisms in the framework structure of Gd Fe(CN)_(6).