Strong anharmonicity-assisted low lattice thermal conductivities and high thermoelectric performance in double-anion Mo_(2)AB_(2)(A=S,Se,Te;B=Cl,Br,I)semiconductors

The thermoelectric properties of layered Mo_(2)AB_(2)(A=S,Se,Te;B=Cl,Br,I)materials are systematically investigated by first-principles approach.Soft transverse acoustic modes and direct Mo d–Mo d couplings give rise to strong anharmonicities and low lattice thermal conductivities.The double anions with distinctly different electronegativities of Mo_(2)AB_(2)monolayers can reduce the correlation between electron transport and phonon scattering,and further benefit much to their good thermoelectric properties.Thermoelectric properties of these Mo_(2)AB_(2)monolayers exhibit obvious anisotropies due to the direction-dependent chemical bondings and transport properties.Furthermore,their thermoelectric properties strongly depend on carrier type(n-type or p-type),carrier concentration and temperature.It is found that n-type Mo_(2)AB_(2)monolayers can be excellent thermoelectric materials with high electric conductivity,σ,and figures of merit,ZT.Choosing the types of A and B anions of Mo_(2)AB_(2)is an effective strategy to optimize their thermoelectric performance.These results provide rigorous understanding on thermoelectric properties of double-anions compounds and important guidance for achieving high thermoelectric performance in multi-anion compounds.

A Model Effective Mass Quantum Anharmonic Oscillator and Its Thermodynamic Characterization

Using a model anharmonic oscillator with asymptotically decreasing effective mass to study the effect of compositional grading on the quantum mechanical properties of a semiconductor heterostructure, we determine the exact bound states and spectral values of the system. Furthermore, we show that ordering ambiguity only brings about a spectral shift on the quantum anharmonic oscillator with spatially varying effective mass. A study of thermodynamic properties of the system reveals a resonance condition dependent on the magnitude of the anharmonicity parameter. This resonance condition is seen to set a critical value on the said parameter beyond which a complex valued entropy which is discussed, emerges.

Phase transition and thermodynamic properties of ThO2： Quasi-harmonic approximation calculations and anharmonic effects

The thermodynamic properties and the phase transition of ThO2 from the cubic structure to the orthorhombic structure are investigated using the first-principles projector-augmented wave method. The vibrational contribution to Helmholtz free energy is evaluated from the first-principles phonon calculations. The anharmonic contribution to quasi-harmonic free energy is accounted for by using an effective method （2010 Phys. Rev. B 81 172301）. The results reveal that at ambient temperature, the phase transition from the cubic phase to the orthorhombic phase occurs at 26.45 GPa, which is consistent with the experimental and theoretical data. With increasing temperature, the transition pressure decreases almost linearly. By comparing the experimental results with the calculation results, it is shown that the thermodynamic properties of ThO2 at high temperature improve substantially after including the anharmonic correction to quasi-harmonic free energy.

Effects of anharmonic lattice distortion on orbital and magnetic orderings in KCuF_3

Lattice, magnetic and orbital structures in KCuF3 are self-consistently determined by our cluster self-consistent field approach based on a spin-orbital-lattice Hamiltonian. Two stable structures are obtained and found to be degenerate, which confirms the presence of the coexistent phases observed experimentally. We clearly show that due to the inherent frustration, the ground state of the system only with the superexchange interaction is degenerate; while the Jahn-Teller distortion, especially the anharmonic effect, stabilizes the orbital ordered phase at about 23% in the x2-y2 orbit and at 77% in the 3z2-r2 orbit. Meanwhile the magnetic moment of Cu is considerably reduced to 0.56μB, and magnetic coupling strengths are highly anisotropic, Jx/Jxy ≈ 18. These results are in good agreement with the experiments, implying that the anharmonic Jahn-Teller effect plays an essential role in stabilising the orbital ordered ground state of KCuF3.

Amplitude-squared squeezing of the generalized odd-even coherent states of the anharmonic oscillator in a finite-dimensional Hilbert space

This paper discusses the properties of amplitude-squared squeezing of the generalized odd-even coherent states of anharmonic oscillator in finite-dimensional Hilbert space. It demonstrates that the generalized odd coherent states do exhibit strong amplitude-squared squeezing effects in comparison with the generalized even coherent states.

Tunable anharmonicity versus high-performance thermoelectrics and permeation in multilayer(GaN)_(1-x)(ZnO)_(x)

Nonisovalent(GaN)_(1-x)(ZnO)_(x)alloys are more technologically promising than their binary counterparts because of the abruptly reduced band gap.Unfortunately,the lack of two-dimensional(2D)configurations as well as complete stoichiometries hinders to further explore the thermal transport,thermoelectrics,and adsorption/permeation.We identify that multilayer(GaN)_(1-x)(ZnO)_(x)stabilize as wurtzite-like Pm-(GaN)_(3)(ZnO)_(1),Pmc2_(1)-(Ga N)_(1)(ZnO)_(1),P3m1-(GaN)_(1)(ZnO)_(2),and haeckelite C2/m-(GaN)_(1)(ZnO)_(3)via structural searches.P3m1-(GaN)_(1)(ZnO)_(2)shares the excellent thermoelectrics with the figure of merit ZT as high as 3.08 at 900 K for the p-type doping due to the ultralow lattice thermal conductivity,which mainly arises from the strong anharmonicity by the interlayer asymmetrical charge distributions.The p–d coupling is prohibited from the group theory in C2/m-(Ga N)_(1)(ZnO)_(3),which thereby results in the anomalous band structure versus Zn O composition.To unveil the adsorption/permeation of H^(+),Na^(+),and OH^(-)ions in AA-stacking configurations,the potential wells and barriers are explored from the Coulomb interaction and the ionic size.Our work is helpful in experimental fabrication of novel optoelectronic and thermoelectric devices by 2D(GaN)_(1-x)(ZnO)_(x)alloys.

Equation of state for solids considering cohesive energy and anharmonic effect and its application to MgO

A simple equation of state （EOS） in wide ranges of pressure and temperature is constructed within the MieGruneisen Debye framework. Instead of the popular Birch-Murnaghan and Vinet EOS, we employ a five-parameter cold energy expression to represent the static EOS term, which can correctly produce cohesive energy without any spurious oscillations in the extreme compression and expansion regions, We developed a Pade approximation-based analytic Debye quasiharmonic model with high accuracy which improves the performance of EOS in the low temperature region. The anharmonic effect is taken into account by using a semi-empirical approach. Its reasonability is verified by the fact that the total thermal pressure tends to the lowest-order anharmonic expansion in the literature at low temperature, and tends to ideal-gas limitation at high temperature, which is physically correct. Besides, based on this approach, the anharmonic thermal pressure can be expressed in the Griineisen form, which is convenient for applications. The proposed EOS is used to study the thermodynamic properties of MgO including static and shock compression conditions, and the results are very satisfactory as compared with the experimental data.

Generation-channel interference of high-order harmonics of an anharmonic oscillator driven by bi-chrime laser fields and its mechanism

A method to describe the generation channels of high-order harmonics is proposed. According to this method, the mechanism of generation-channel interference of high-order harmonics is revealed clearly. We take the anharmonic oscillator driven by bi-chrome fields as an example to illustrate that this method can be used to understand the effect of generation-channel interference.

Critical rotation of an anharmonically trapped Bose-Einstein condensate

We consider rotational motion of an interacting atomic Bose-Einstein condensate （BEC） with both two- and three- body interactions in a quadratic-plus-quartic and harmonic-plus-Gaussian trap. By using the variational method, the influence of the three-body interaction and the anharmonicity of the trap on the lowest energy surface mode excitation and the spontaneous shape deformation （responsible for the vortex formation） in a rotating BEC is discussed in detail. It is found that the repulsive three-body interaction helps the formation of the vortex and reduces the lowest energy surface mode frequency and the critical rotational frequency of the system. Moreover, the critical rotational frequency for the vortex formation in the harmonic-plus-Gaussian potential is lower than that in the quadratic-plus-quartic potential.

High-Fidelity Hugoniots of α Phase RDX Solid from High-Quality Force Field with Thermal,Zero-Point Vibration,and Anharmonic Effects

It is shown that the introduction of thermal effect, zero-point vibration, and phonon anharmonicity to a high quality and first-principle-Sased force field （atomic potential） results in a significant improvement in predict- ing the densities for the α phase crystalline hexahydro-1,3,5-trinitro-l,3,5-triazine （RDX）, and derivation of its high-fidelity Hugoniot locus and Mie-Grfineisen equation of state covering a very wide range of pressures and temperatures. This work can be used to efficiently and accurately predict the thermophysical properties of solid explosives over the pressures and temperatures to which they are subjected, which is a long-standing issue in the field of energetic materials.

Anharmonic Potentials Analysis through the Floquet Representation

We propose an approach based on Floquet theorem combined with the resonating averages method (RAM), to solve the time-dependent Schrödinger equation with a time-periodic Hamiltonian. This approach provides an alternative way to determine directly the evolution operator, and then we deduct the wave functions and the corresponding quasi-energies, of quantum systems. An application is operated for the driven cubic or/and quatric anharmonic as well as for the Morse potential. Comparisons of our results with those of other authors are discussed, and numerical evaluations are performed, to determine the dissociation energy of (HCl) and (CO) molecules.

Coupled Two-Dimensional Atomic Oscillation in an Anharmonic Trap

In atomic dynamics, oscillation Mong different axes can be studied separately in the harmonic trap. When the trap is not harmonic, motion in different directions may couple together. In this work, we observe a two- dimensional oscillation by exciting atoms in one direction, where the atoms are transferred to an anharmonic region. Theoretical calculations are coincident to the experimental results. These oscillations in two dimensions not only can be used to measure trap parameters but also have potential applications in atomic interferometry and precise measurements.

Implementation of ternary Shor's algorithm based on vibrational states of an ion in anharmonic potential

It is widely believed that Shor＇s factoring algorithm provides a driving force to boost the quantum computing research.However, a serious obstacle to its binary implementation is the large number of quantum gates. Non-binary quantum computing is an efficient way to reduce the required number of elemental gates. Here, we propose optimization schemes for Shor＇s algorithm implementation and take a ternary version for factorizing 21 as an example. The optimized factorization is achieved by a two-qutrit quantum circuit, which consists of only two single qutrit gates and one ternary controlled-NOT gate. This two-qutrit quantum circuit is then encoded into the nine lower vibrational states of an ion trapped in a weakly anharmonic potential. Optimal control theory（OCT） is employed to derive the manipulation electric field for transferring the encoded states. The ternary Shor＇s algorithm can be implemented in one single step. Numerical simulation results show that the accuracy of the state transformations is about 0.9919.

New approach for deriving the exact time evolution of the density operator for a diffusive anharmonic oscillator and its Wigner distribution function

Using thermal entangled state representation,we solve the master equation of a diffusive anharmonic oscillator（AHO） to obtain the exact time evolution formula for the density operator in the infinitive operator-sum representation.We present a new evolution formula of the Wigner function（WF） for any initial state of the diffusive AHO by converting the WF calculation into an overlap between two pure states in an enlarged Fock space.It is found that this formula is very convenient in investigating the WF＇s evolution of any known initial state.As applications,this formula is used to obtain the evolution of the WF for a coherent state and the evolution of the photon-number distribution of diffusive AHOs.

Theory of Electron Density of States of High Temperature Impurity Induced Anharmonic Superconductors

The expression for the electron density of states (EDOS) of high temperature superconductors (HTS) has been derived taking the disorder and anharmonicity effects as a central problem. This has been dealt with the help of double time thermodynamic Green’s function theory for electrons via a generalized Hamiltonian which consists of the contribution due to 1) unperturbed electrons;2) unperturbed phonons;3) isotopic impurities;4) anharmonicities (no BCS type Hamiltonian has been taken up in the formulation);and 5) electron-phonon interactions. The renormalization effects and emergence of pairons appears as a unique feature of the theory and dependence of EDOS on impurity concentration and temperature has been discussed in details with special reference to the HTS.

Electronic origin of the unusual thermal properties of copper-based semiconductors:The s-d coupling-induced large phonon anharmonicity

Copper(Cu)-based materials(such as cuprates,Cu chalcogenides,and Cu halides)often exhibit unusual properties such as superconductivity,ultralow thermal conductivity,and superionicity.However,the electronic origin of these unusual behaviors remains elusive.In this study,we demonstrate that the high-lying occupied 3d orbital of Cu causes a strong s-d coupling with its unoccupied 4s state when local symmetry is reduced.This leads to strong phonon anharmonicity and is responsible for these intriguing properties.For example,during thermal transport,symmetry-controlled s-d coupling can substantially lower the lattice potential barrier,thereby enhancing the anharmonicity and scattering between phonons and ultimately significantly reducing lattice thermal conductivity.We confirmed this understanding with Raman spectra measurements,which demonstrated a remarkable red shift in the phonon vibrational frequency with an increase in the temperature of Cu-based semiconductors.Our study shows that the cause of phonon anharmonicity is related to the fundamental electronic structures,which can also explain other unusual physical properties of the Cu compounds.

Band modification towards high thermoelectric performance of SnSb_(2)Te_(4) with strong anharmonicity driven by cation disorder

As a typical (IV–VI)_(x)(V_(2)VI_(3))_(y) compound, the tetradymite-like layered SnSb_(2)Te_(4) -based compounds have attracted increasing attention in the thermoelectric community owing to the intrinsically low lattice thermal conductivity. Nevertheless, the effect of cations disorder on the inherent physical characteristics remains puzzling, and its inferior Seebeck coefficient is the bottleneck to achieving high thermoelectric performance. In this work, the thermoelectric properties of polycrystalline In_(x)Sn_(1−x)Sb_(2)(Te_(1−y)Se_(y))_(4) (0≤x≤0.1,0≤y≤0.15) samples are comprehensively investigated. In conjunction with the calculated band structure and experimental results, the Seebeck coefficient and power factor are markedly improved after the introduction of indium and selenium, which originates from the combined effects of the emergent resonant states and converged valence bands along with optimal carrier concentration. Additionally, compared with the ordered lattice structure, the disordered cations occupancy in SnSb_(2)Te_(4) further strengthens lattice anharmonicity and reduces phonon group velocity verified by first-principles calculations, securing intrinsically low lattice thermal conductivity. Finally, a record zT value of ∼0.6 at 670 K and an average zT of ∼0.4 between 320 and 720 K are obtained in the In0.1 Sn0.9 Sb2 Te3.4 Se0.6 sample, being one of the highest zT values among SnSb2 Te4 -based materials. This work not only demonstrates that SnSb2 Te4 -based compounds are promising thermoelectric candidates, but also provides guidance for the promotion of thermoelectric performance in a broad temperature range.

Phonon transport properties of Janus Pb_(2)XAs(X=P,Sb,and Bi)monolayers:A DFT study

Grasping the underlying mechanisms behind the low lattice thermal conductivity of materials is essential for the efficient design and development of high-performance thermoelectric materials and thermal barrier coating materials.In this paper,we present a first-principles calculations of the phonon transport properties of Janus Pb_(2)PAs and Pb_(2)SbAs monolayers.Both materials possess low lattice thermal conductivity,at least two orders of magnitude lower than graphene and h-BN.The room temperature thermal conductivity of Pb_(2)SbAs(0.91 W/m K)is only a quarter of that of Pb_(2)PAs(3.88 W/m K).We analyze in depth the bonding,lattice dynamics,and phonon mode level information of these materials.Ultimately,it is determined that the synergistic effect of low group velocity due to weak bonding and strong phonon anharmonicity is the fundamental cause of the intrinsic low thermal conductivity in these Janus structures.Relative regular residual analysis further indicates that the four-phonon processes are limited in Pb_(2)PAs and Pb_(2)SbAs,and the three-phonon scattering is sufficient to describe their anharmonicity.In this study,the thermal transport properties of Janus Pb_(2)PAs and Pb_(2)SbAs monolayers are illuminated based on fundamental physical mechanisms,and the low lattice thermal conductivity endows them with the potential applications in the field of thermal barriers and thermoelectrics.

Anharmonicity induced thermal modulation in stressed graphene

Thermal properties are essentially decided by atomic geometry and thus stress is the most direct way for manipulating. In this paper, we investigate stress modulation of thermal conductivity of graphene by molecular dynamics simulations and discuss the underlying microscopic mechanism. It is found that thermal conductivity of flexural-free graphene increases with compression and decreases with strain, while thermal conductivity of flexural-included graphene decreases with both compression and strain. Such difference in thermal behavior originates from the changes in the anharmonicity of the interatomic potential, where the wrinkle scattering is responsible for the thermal conductivity diminishment in flexural-included graphene under strain. By comparing the results obtained from the Tersoff and AIREBO potentials, it is revealed that the degree of the symmetry of interatomic potential determines the thermal conductivity variation of graphene. Our results indicate that the symmetry of interatomic potential should be taken into careful consideration in constructing the lattice model of graphene.

In-situ High-Temperature XRD and FTIR for Calcite, Dolomite and Magnesite: Anharmonic Contribution to the Thermodynamic Properties

In-situ powder X-ray diffraction(XRD) and Fourier transform infrared(FTIR) spectra were measured on the natural crystals of calcite(Ca0.996 Mg0.004 CO3), dolomite(Ca0.497 Mg0.454 Fe0.046 Mn0.003 CO3) and magnesite(Mg0.988 Ca0.010 Fe0.002 CO3), with a temperature up to 796 K. The thermal expansion coefficients were evaluated for these carbonate minerals, resulting in the values of 2.7×10^-5, 3.3×10^-5 and 3.5×10^-5 K^-1 for calcite, dolomite and magnesite, respectively. The magnitude of these coefficients is in the same order as those for the isothermal and elastic moduli of these carbonates(e.g., calcite<dolomite<magnesite). The IR-active internal modes of the CO3 group systematically shift to lower frequencies at elevated temperature, and the isobaric(γi P) and isothermal(γi T) Grüneisen parameters for the internal modes are generally smaller than 0.5. The corresponding anharmonic parameters(ai) are typically within the range of-1.5–+1×10^-5 K^-1, which are significantly smaller in magnitude than those for the external modes. We also calculate the thermodynamic properties(internal energy, heat capacities and entropy) at high temperatures for these carbonates, and the anharmonic contribution to thermodynamics shows an order of calcite>dolomite>magnesite. The Debye model(harmonic approximation) would be valid for magnesite to simulating the thermodynamic properties and isotope fractionation β-factor at high P-T condition.