Thermodynamics of phonon-stabilized Fermi distributions with application to uranium

Since phonons are built on the free energy of electrons, their frequencies can be altered by thermal electronic excitations, implying that thermal electronic excitations can alter the phonon entropy. The effect of this extra phonon entropy on electronic distribution functions and thermodynamic properties is calculated in the limit of classical vibrations. The phonon entropy stabilizes electrons above the Fermi level by more than the usual k _B T. The thermodynamic coupling of electron and phonon degrees of freedom allows far more heat capacity than in equivalent independent systems. The method developed is used to explain uranium data from the literature.     

A first-principle study of Os-based compounds: Electronic structure and vibrational properties

The electronic structure, elastic, and phonon properties of OsM (M=Hf, Ti, Y and Zr) compounds are studied using first-principles calculations. Elastic constants of OsY and specific heat capacity of OsM (M=Hf, Ti, Y, and Zr) are reported for the first time. The predicted equilibrium lattice constants are in excellent agreement with experiment. The calculated values of bulk moduli are considerably high but are much smaller than that of Osmium, which is around 400 GPa. The phase stability of the OsM (M=Hf, Ti, Y and Zr) compounds were studied by DOS calculations and the results suggest that OsY is unstable in the B2 phase. The brittleness and ductility properties of OsM (M=Hf, Ti, Y and Zr) are determined. OsM (M=Hf, Ti, Y and Zr) compounds are predicted to be ductile materials. The electronic structure and phonon frequency curves of OsM (M=Hf, Ti, Y and Zr) compounds are obtained. The position of Fermi level of these systems was calculated and discussed in terms of the pseudo gaps. The finite and small DOS at the Fermi level 0.335, 0.375, 1.063, and 0.383 electrons/eV for OsHf, OsTi, OsY, and OsZr, respectively, suggest that OsM (M=Hf, Ti, Y and Zr) compounds are weak metals.     

First principles study and comparison of vibrational and thermodynamic properties of XBi(X= In,Ga, B,Al)

In the present work, vibrational and thermodynamic properties of XBi(X = B, Al, Ga, In) compounds are compared and investigated. The calculation is carried out using density functional theory(DFT) within the generalized gradient approximation(GGA) in a plane wave basis, with ultrasoft pseudopotentials. The lattice dynamical properties are calculated using density functional perturbation theory(DFPT) as implemented in Quantum ESPRESSO(QE) code. Thermodynamic properties involving phonon density of states(DOS) and specific heat at constant volume are investigated using quasiharmonic approximation(QHA) package within QE. The phonon dispersion diagrams for InBi, GaBi, BBi, and AlBi indicate that there is no imaginary phonon frequency in the entire Brillouin zone, which proves the dynamical stability of these materials. BBi has the highest thermal conductivity and InBi has the lowest thermal conductivity. AlBi has the largest and GaBi has the smallest reststrahlen band which somehow suggests the polar property of XBi materials. The phonon gaps for InBi, GaBi, BBi and AlBi are about 160 cm~(-1), 150 cm~(-1), 300 cm~(-1), and 150 cm~(-1), respectively. For all compounds,the three acoustic modes near the gamma point have a linear behavior. C_V is a function of T~3 at low temperatures while for higher temperatures it asymptotically tends to a constant as expected.     

重费米子超导PuMGa5(M=Co,Rh)结构、电子和热力学性质的第一性原理研究

基于第一性原理的PBEsol+U方法研究PuCoGa₅和PuRhGa₅的晶体结构、弹性、电子性质、声子谱以及热力学性质。PBEsol+U方法考虑Pu-5f的库伦排斥作用U和Hund交换相关作用J。计算结果表明,PuCoGa₅和PuRhGa₅在PBEsol+U方法下的基态性质（包括晶格参数和原子占位）与实验数据吻合较好,且力学判据和声子谱均表明在零温和零压条件下PuCoGa₅和PuRhGa₅的基态结构是稳定的;特别地,PuRhGa₅的5f电子在费米能级附近的定域性明显强于PuCoGa₅,这可能是PuCoGa₅的超导临界转变温度高于PuRhGa₅的重要原因。此外,还研究了PuCoGa₅与PuRhGa₅的赫姆霍兹自由能、熵、内能和等容摩尔热容随温度的变化。     

Adiabatic electron-phonon interaction and high-temperature thermodynamics of A15 compounds

Inelastic neutron scattering was used to measure the phonon densities of states of the A15 compounds V3Si, V3Ge, and V3Co at temperatures from 10 to 1,273 K. It was found that phonons in V3Si and V3Ge, which are superconducting at low temperatures, exhibit an anomalous stiffening with increasing temperature, whereas phonons in V3Co have a normal softening behavior. First-principles calculations show that this anomalous increase in phonon frequencies at high temperatures originates with an adiabatic electron-phonon coupling mechanism. The anomaly is caused by the thermally induced broadening of sharp peaks in the electronic density of states of V3Si and V3Ge, which tends to decrease the electronic density at the Fermi level. These results show that the adiabatic electron-phonon coupling can influence the phonon thermodynamics at temperatures exceeding 1,000 K.     

Positive vibrational entropy of chemical ordering in FeV

Inelastic neutron scattering and nuclear resonant inelastic x-ray scattering were used to measure phonon spectra of FeV as a B2 ordered compound and as a bcc solid solution. The two data sets were combined to give an accurate phonon density of states, and the phonon partial densities of states for V and Fe atoms. Contrary to the behavior of ordering alloys studied to date, the phonons in the B2 ordered phase are softer than in the solid solution. Ordering increases the vibrational entropy by +0.22±0.03 kB/atom, which stabilizes the ordered phase to higher temperatures. First-principles calculations show that the number of electronic states at the Fermi level increases upon ordering, enhancing the screening between ions, and reducing the interatomic force constants. The effect of screening is larger at the V atomic sites than at the Fe atomic sites.     

Electronic topological transition in metastable Al-Ge solid solutions

Al-rich Al-Ge solid solutions synthesized under high pressure demonstrate physical properties strikingly different from those of pure Al. In particular, enhanced superconductivity temperature (T_c), anomalies in the phonon spectra and decrease of the Debye temperature have been observed. We show from first-principles, based on calculations of the electronic spectra and Fermi surfaces of Al-Ge substitutional solid solutions, that an electronic topological transition (ETT) takes place in the system. We predict anomalies in transport properties to be revealed experimentally for Al-Ge solid solutions with the Ge concentration ≈10 at.%. The influence of the ETT on the thermodynamic properties of the system is discussed and, in particular, concentration dependence of the Debye temperature is reproduced in good agreement with experiment.     

The influence of 3d-metal alloy additions on the elastic and thermodynamic properties of CuPd3

Embedded-atom method （EAM） potentials are used to investigate the effects of alloying （e.g. 3d-metals） on the trends of elastic and thermodynamic properties for CuPd3 alloy. Our calculated lattice parameter, cohesive energy, and elastic constants of CuPd3 are consistent with the available experimental and theoretical data. The results of elastic constants indicate that all these alloys are mechanically stable. Further mechanical behavior analysis shows that the additions of Cr, Fe, Co, and Ni could improve the hardness of CuPd3 while V could well increase its ductility. Moreover, in order to evaluate the thermodynamic contribution of 3d-metals, the Debye temperature, phonon density of states, and vibrational entropy for CuMPd6 alloy are also investigated.     

Elastic,vibrational, and thermodynamic properties of Sr_(10)(PO_4)_6F_2 and Ca_(10)(PO_4)_6F_2 from first principles

The electronic, elastic, vibrational, and thermodynamic properties of Sr_(10)(PO_4)_6F_2(Sr-FAP) and Ca_(10)(PO_4)_6F_2(CaFAP) are systematically investigated by the first-principles calculations. The calculated electronic band structure indicates that the Sr-FAP and Ca-FAP are insulator materials with the indirect band gap of 5.273 eV and 5.592 eV, respectively. The elastic constants are obtained by the "stress–strain" method, and elastic modulus are further evaluated and discussed. The vibrational properties, including the phonon dispersion curves, the phonon density of states, the Born effective charge, and associated longitudinal optical and transverse optical(LO–TO) splitting of optical modes, as well as the phonon frequencies at zone-center are obtained within the linear-response approach. Substitution of Ca by Sr causes phonon frequencies to shift to lower values as expected due to the mass effect. Additionally, some phonon-related thermodynamic properties, such as Helmholtz free energy F, internal energy E, entropy S, and specific heat C_V of Sr-FAP and Ca-FAP are predicted with the harmonic approximation. The present calculated results of two apatites are consistent with the reported experimental and theoretical results.     

Physical properties of the cubic spinel LiMn2O4

We have performed an ab initio study of structural, electronic, magnetic, vibrational and thermal properties of the cubic spinel LiMn₂O₄ by employing the density functional theory, the linear-response formalism, and the plane-wave pseudopotential method. An analysis of the electronic structure with the help of electronic density of states shows that the density of states at the Fermi level (N (E_F)) is found to be governed by the Mn 3d electrons with some contributions from the 2p states of O atoms. It is important to note that the contribution of Mn 3d states to N(_EF)$N\left(E_F\right)$ is as much as 85%. From our phonon calculations, we have obtained that the main contribution to phonon density of states (below 250 cm⁻¹) comes from the coupled motion of Mn and O atoms while phonon modes between 250 cm⁻¹ and 375 cm⁻¹ are characterized by the vibrations of all the three types of atoms. The contribution from Li increases rapidly at higher frequency (above 375 cm⁻¹) due to the light mass of this atom. Finally, the specific heat and the Debye temperature at 300 K are calculated to be 249.29 J/mol K and 820.80 K respectively.     

Co_(2~-)基Heusler合金Co_2FeAl_(1–x)Si_x(x=0.25,x=0.5,x=0.75)的结构、电子结构及热电特性的第一性原理研究

运用基于密度泛函理论的第一性原理方法,对Co_2FeAl_(1–x)Si_x(x=0.25, 0.5, 0.75)系列Heusler合金的电子结构、四方畸变、弹性常数,声子谱以及热电特性进行了计算研究.结果显示, Co_2FeAl_(1–x)Si_x系列合金的电子结构均为半金属特性,向下自旋态(半导体性)均呈现良好的热电特性,并且随着硅原子浓度的增加功率因子随之增加.计算的声子谱不存在虚频,均满足动力学稳定性条件,弹性常数均满足玻恩稳定性条件,机械稳定性均良好.随着晶格常数c/a的比值变化,体系的能量最低点均出现在c/a=1处,即结构稳定性不随畸变度c/a的变化而变化,说明不存在马氏体相变.此系列合金薄膜的电子结构呈现较高的自旋极化率,在替代浓度x=0.75时自旋极化率达到100%,且当x=0.75时薄膜在畸变度c/a=1.2时存在马氏体相变.随着晶格畸变度的改变,总磁矩也发生变化,且主要由Fe和Co两种过渡金属原子的磁矩变化所决定.     

Spin asymmetry and s-electron itinerancy in Co/X (X=Co,Cu, V and Ta) multilayers: their dependence on the electronegativity of non-magnetic layers

The electronic structure and magnetic properties of the Co at the Co/X (X=Co, Cu, V and Ta) interfaces have been studied by first-principle discrete variational method. We have found that the spin asymmetry and the s-electron itinerancy of the Co interface layer in the Co/X systems are strongly dependent on the electronegativity of the non-magnetic layers. A large difference in the electronegativity between the non-magnetic and Co layers is unfavorable both for s-electron itinerancy and for the spin exchange split of DOS at the Fermi level. Further study on charge density has revealed that a bond is formed across the Co/V and Co/Ta interfaces.     

Au(111)表面吸附单个八乙基钴卟啉分子的电子态和输运性质调控

通过低温超高真空扫描隧道显微镜及其谱学方法研究并展示了分子配体在调控表面吸附的单个八乙基钴卟啉(CoOEP)分子的电子态和输运性质中的重要作用. 通过单分子剪裁可以脱去该分子外围的甲基, 并在中心钴原子的微分电导谱中观察测到d轨道共振到近藤共振的演变. 实验结果结合第一性原理的理论计算研究表明, 在脱去甲基前后中心钴原子的化学环境和磁矩均未发生显著变化, 这一演变可以通过一个简化模型来阐释并被归结为脱去甲基后分子配体与衬底成键改变了体系隧穿参数所导致. 此外, 实验结果表明CoOEP分子配体的输运性质可受到分子间距离和范德华相互作用的显著调控. 在CoOEP低聚体中位于分子之间的乙基被抬高, 同时在其微分电导谱谱中0–0.8 V区域内新出现一个强的共振峰. 这一新的共振峰表现出等间距的多峰细节, 其峰间距与卟啉环和乙基之间的C–C键伸缩模式能量符合. 这一新共振峰的出现被归结为由于分子局部与衬底耦合减弱形成双结隧穿体系所导致的振子态隧穿峰.     

Lattice dynamics in ferromagnetic invar alloys

The lattice dynamical properties of the Invar alloys Fe₆₅Ni₃₅ and Fe₇₂Pt₂₈ are discussed. The experiments on the lattice vibration by inelastic neutron scattering have shown an apparent correlation of phonon anomalies with the ferromagnetic long range order. The elastic softening below the Curie temperature is attributed to the dynamical aspects, at least for the [ςς0]TA₁ mode. The lattice dynamical features are derived from the electronic structure of the Invar alloys. They are consistent with the theoretical model that Invar characters are closely related to the detailed band structure of the d electrons near the Fermi level. The present studies indicate significant contributions of phonon anomalies to the Invar problem.     

PdY合金及其一氢化物分子结构及热力学函数的研究

本文利用B3LYP的密度泛函方法对PdY、 PdYH的分子结构进行了优化,得到PdY最稳定的电子态为2∑,RPdY=0.2418 nm,ωe=249.66cm-1,De=2.75eV.PdYH最稳定构型为Cs,1A'态,RPdY=0.243 0 nm,RYH=0.197 4nm,∠PdYH=116.54°,谐振频率v1(a')=1 450.83cm-1,v2(a')=351.21cm-1,v3(a')=243.71cm-1,离解能De(PdYH)为5.64 eV.并以气态分子总能量中的振动能Ev代替分子处于固态时的振动能,以电子运动和振动运动熵SEv代替分子处于固态的熵的近似方法计算了PdY与氢及其同位素反应的△Hθ、△Sθ、△Gθ及氢化反应平衡压力,得出PdYH(S)的生成焓为60.32kJ·mol-1.     

The nature of isostructural spinodal decomposition in the Al-Zn system

The electronic structure and thermodynamic properties of disordered Al-Zn alloys are investigated in the coherent potential approximation by the KKR-ASA method. Analysis of the electronic density of states and the Fermi surfaces of disordered alloys reveals the presence of eight electronic topological transitions in the concentration interval from 0 to 70 at. % Zn. It is shown that the passage of the Fermi level through two minima of the density of states, which are due to the superposition of different types of electronic topological transitions, gives rise to singularities in the concentration dependence of the second derivative of the thermodynamic potential at points corresponding to the boundaries of the region of isostructural decomposition of the high-temperature solid solution, according to the phase diagram of the Al-Zn system. Fiz. Tverd. Tela (St. Petersburg) 39, 593–596 (April 1997)     

M@C_(20)H_(20)(M=Sc,V,Cr,Mn,Fe,Co,Ni)几何结构和电子性质的理论研究

采用密度泛函理论(DFT)中的广义梯度近似(GGA)方法对M@C_(20)H_(20)(M=Sc,V,Cr,Mn,Fe,Co,Ni)几何结构和电子性质进行了计算研究.几何结构优化发现,过渡金属原子M内掺到C_(20)H_(20)笼时,都稳定于碳笼中心.能隙和内掺能计算发现,M@C_(20)H_(20)的热力学稳定性随着M原子序数的增大而逐渐减弱,内掺M原子使得其动力学稳定性大幅度下降,但是其中Ni@C_(20)H_(20)结构仍然具有良好的热力学和动力学稳定性,其有望在实验中被成功合成出来.电子性质研究发现,随着M原子序数的逐渐增大,M原子对M@C_(20)H_(20)前线轨道的贡献也越来越大,M@C_(20)H_(20)(M=Sc,V,Cr,Mn,Fe,Co)都具有一定的磁矩,而Ni@C_(20)H_(20)为闭壳层结构,磁矩为零.     

Electronic structure and magnetic properties of metastable SmCo_7 compound

1 Introduction The rare-earth transition-metal intermetallic compounds have been widely investi-gated for many years, among them the Sm-Co series compounds with 1:5 and 2:17 crys-tal structures. These compounds have been used as sintered and bonded permanent magnets since the 1960s[1,2]. Interest recently has been focused on the TbCu7-type struc-ture Sm-Co intermetallic compounds with a strong uniaxial magnetocrytalline anisot-ropy and a low temperature coefficient (β = ?0.11%)[3―6] due t…     

Studies of high-temperature electron–phonon interactions with inelastic neutron scattering and first-principles computations

Several recent studies of phonons combining inelastic neutron scattering and first-principles calculations are summarized. Inelastic neutron scattering was used to measure the phonon densities of states of the A15 compounds V₃Si, V₃Ge, and V₃Co at temperatures from 10 K to 1273 K. It was found that phonons in V₃Si and V₃Ge, which are superconducting at low temperatures, exhibit an anomalous stiffening with increasing temperature, whereas phonons in V₃Co have a normal softening behavior. Additional measurements of the phonon DOS of BCC V alloys were performed, and it was found that a stiffening anomaly present in pure V is suppressed upon introduction of extra d-electrons by alloying. First-principles calculations of the electronic and phonon densities of states show that in both these systems, the anomalous phonon stiffening originates with an adiabatic electron–phonon coupling mechanism. The anomaly is caused by the thermally-induced broadening of sharp peaks in the electronic density of states, which tends to decrease the electronic density at the Fermi level. These results illustrate how the combined use of first-principles calculations and inelastic neutron scattering provides powerful insights into couplings of excitations in condensed-matter.