Entropy and phase diagram of valence transition

The electronic and lattice entropies associated with the valence transition are estimated. The electronic entropy in metallic phase is evaluated based on the model which includes the mixing between ?-level and d-band states, and the d-band superimposes the hybridized ?-level. The quasiharmonic approximation together with the Debye approximation are used to calculate the lattice entropy. For the first order transition occurring at low temperature the entropy of semiconducting phase is found to be lower than that of metallic phase. The reverse situation is obtained for high transition temperature. This explains the experimental fact that the slope of the phase boundary of valence transition in SmS changes its sign with temperature. The specific heat calculated in this model shows a broad maximum at low temperature.     

Superfluid phase transition in two-dimensional excitonic systems

We study the superfluid phase transition in the two-dimensional (2D) excitonic system. Employing the extended Falicov–Kimball model (EFKM) and considering the local quantum correlations in the system composed of conduction band electrons and valence band holes we demonstrate the existence of the excitonic insulator (EI) state in the system. We show that at very low temperatures, the particle phase stiffness in the pure-2D excitonic system, governed by the non-local cross correlations, is responsible for the vortex–antivortex binding phase-field state, known as the Berezinskii–Kosterlitz–Thouless (BKT) superfluid state. We demonstrate that the existence of excitonic insulator phase is a necessary prerequisite, leading to quasi-long-range order in the 2D excitonic system.     

The model of ultrafast light-induced insulator-metal phase transition in VO2

Ultrafast light-induced insulator-metal phase transitions (PT) in VO₂ thin films was studied with use of a pump-probe technique. The theoretical and experimental study of PT kinetics shows that the PT could be realized via an intermediate state. The relaxation processes after optical pumping are dependent on pump energy. The excitonic controlled model for such type of PT is proposed. The main channel for the ultrafast light-induced PT is the resonant transition between excited states of correlated vibronic Wannier-Mott excitons (WME) in insulator phase and the unoccupied excited states in metallic phase. During this process an equilibrium local distortion occurred. According to the proposed model the experimental observation of the drastic temperature- and pump power- dependent relaxation processes could be interpreted.     

Excitonic insulator: dependence of energy gap width on carrier density

On the basis of the Ashcroft empty core model potential, the equation for the constant of Coulomb interaction in the theory of excitonic insulator is modified. It is shown that in this case the dependence of the energy gap width on the charge carrier density obeys the Mott criterion in the limit of low densities. The conformity of the theory with some experimental data concerning metal–insulator phase transitions in doped semiconductors and transition metal compounds is discussed.     

The excitonic insulator route through a dynamical phase transition induced by an optical pulse

We consider a dynamical phase transition induced by a short optical pulse in a system prone to thermodynamical instability. We address the case of pumping to excitons whose density contributes directly to the order parameter. To describe both thermodynamic and dynamic effects on equal footing, we adopt a view of the excitonic insulator for the phase transition and suggest a formation of the Bose condensate for the pumped excitons. The work is motivated by experiments in donor–acceptor organic compounds with a neutral- ionic phase transition coupled to the spontaneous lattice dimerization and to charge transfer excitons. The double nature of the ensemble of excitons leads to an intricate time evolution, in particular, to macroscopic quantum oscillations from the interference between the Bose condensate of excitons and the ground state of the excitonic insulator. The coupling of excitons and the order parameter also leads to self-trapping of their wave function, akin to self-focusing in optics. The locally enhanced density of excitons can surpass a critical value to trigger the phase transformation, even if the mean density is below the required threshold. The system is stratified in domains that evolve through dynamical phase transitions and sequences of merging. The new circumstances in experiments and theory bring to life, once again, some remarkable inventions made by L.V. Keldysh.     

Competition between phase separation and "Classical" intermediate valence in an exactly solved model

The exact solution of the spin-1 / 2 Falicov-Kimball model on an infinite-coordination Bethe lattice is analyzed in the regime of "classical" intermediate valence. We find that (i) either phase separation or a direct metal-insulator transition precludes intermediate valence over a large portion of the phase diagram, and (ii) within the intermediate valence phase, only continuous transitions are found as functions of the localized f-electron energy or temperature.     

Concentration model of semiconductor-metal phase transitions in SmS

Model calculations explaining the mechanism of the semiconductor-metal phase transition in SmS are carried out. The model, slightly modified, draws upon methods employed earlier to account for the concentration mechanism of piezoelectric resistance and thermovoltaic effect in SmS. The stable results are obtained from calculations for the phase transition pressure under hydrostatic compression (P _c ～ 700 MPa at T = 300 K). On this basis, it is concluded that the 4f levels of samarium ions and their excited states determine the value of P _c . The proposed model is universal in character and can be applied to calculations of other effects in SmS, which are associated with Mott transitions and are accompanied by collective carrier delocalization.     

Evidence for an excitonic insulator phase in 1T-TiSe2

We present a new high-resolution angle-resolved photoemission study of 1T-TiSe2 in both its room-temperature, normal phase and its low-temperature, charge-density wave phase. At low temperature the photoemission spectra are strongly modified, with large band renormalizations at high-symmetry points of the Brillouin zone and a very large transfer of spectral weight to backfolded bands. A calculation of the theoretical spectral function for an excitonic insulator phase reproduces the experimental features with very good agreement. This gives strong evidence in favor of the excitonic insulator scenario as a driving force for the charge-density wave transition in 1T-TiSe2.     

The role of fluctuations in mixed valence compounds

Previous renormalization group results for a simple spinless mixed valence model yielded large intersite ?-electron correlations if extended coherent hybridization mixed valence states are assumed. We simulate these correlations by an ?-level energy distribution and analyze its consequences. It is seen that a relatively small distribution width already smears the coherent hybridization gap leading to a lattice of essentially independent resonant levels.     

Mixed valency and phase transitions at the (001) SmS surface

A model for mixed valency and phase transitions at (001) SmS is suggested. Focussing on the electron-lattice coupling as a mechanism potentially responsible for both phenomena, the problem of the semi-infinite crystal is factorized and reduced to the investigation of a low-dimensional effective Hamiltonian matrix. Surface geometry and electronic structure are obtained simultaneously by numerical minimization of the free energy. The possible appearance of mixed valency and of phase transitions confined to the surface region and involving relaxed or reconstructed geometry is demonstrated.     

The effect of pressure on lattice parameter,magnetic susceptibility and reflectivity of SmS

The lattice parameter of SmS single crystals has been measured under hydrostatic pressure up to 70 kbar. The fit for the metallic phase by means of the Birch equation gives an unusually large pressure derivative of the bulk modulus B' = 11 and hence a large pressure dependence of B. No change in the nonmagnetic intermediate valence state of Sm is observed up to 24 kbar as concluded from our magnetic susceptibility measurements. Reflectivity measurements under hydrostatic pressure p > 6.5 kbar show a small plasma edge shift (～0.08 eV) towards lower energy upon cooling from 77 to 4.2 K. Hence the low temperature resistivity anomaly is attributed to an enhanced conduction electron scattering.     

Observation of selection rules and restricted valence band self convolution for the KVV Auger transition of alkali graphite intercalation compounds

The Auger spectrum of the KVV transition in alkali graphite intercalation compounds (AGIC's) gives unambiguous evidence that the electron states from the alkali metals in the valence band of the compound form a narrow structure in the KVV Auger spectrum which corresponds to the self convolution of these states and that they are not convoluted with the whole valence band. This observation shows that strong matrix element effects or selection rules for KVV Auger transitions have to be taken into account.     

Elementary excitations in correlated electron systems: Excitonic waves

The dispersion relation for the collective elementary excitations of an excitonic insulator are derived. It is argued that these excitonic waves play an important role in distortive transitions (of transition metal oxides among others) and in surface reconstruction.     

Behavior of the antiferromagnetic phase transition near the fermion condensation quantum phase transition in YbRh2Si2

Low-temperature specific-heat measurements on YbRh₂Si₂ at the second order antiferromagnetic (AF) phase transition reveal a sharp peak at TN=72 mK. The corresponding critical exponent α turns out to be α=0.38, which differs significantly from that obtained within the framework of the fluctuation theory of second order phase transitions based on the scale invariance, where α?0.1. We show that under the application of magnetic field the curve of the second order AF phase transitions passes into a curve of the first order ones at the tricritical point leading to a violation of the critical universality of the fluctuation theory. This change of the phase transition is generated by the fermion condensation quantum phase transition. Near the tricritical point the Landau theory of second order phase transitions is applicable and gives α?1/2. We demonstrate that this value of α is in good agreement with the specific-heat measurements.     

Hybridization effect on phase transitions in the Falicov-Kimball model

The Falicov-Kimball model extended by the hybridization between the localized electron states and the conduction band states is studied in Hartree-Fock approximation. Taking into account the periodicity of the system, the occupation number of the localized levels always varies continuously with the level energy for non-vanishing hybridization. This result is in contradiction with earlier mean-field calculations which are not self- consistent for the periodic model. Since first order phase transitions in intermediate valence compounds such as SmS have been observed experimentally, it follows that their explanation needs a more general theoretical frame than the model considered here.     

Critical point wetting in NbH0.31

The local α-α' phase distribution in a thin Nb single crystal loaded with the critical H-concentration was investigated with X-rays. The sample used in the experiment showed a macroscopic hydrogen density mode, leading to a curvature of the whole crystal plate with the α-phase on the concave side and the α'-phase on the convex side. In addition an α-phase wetting layer was found on top of the α'-phase separated from the bulk α'-phase by a mixed α-α' phase region. In a simple model their thickness were determined to about $\text{\$}\text{?}$1.0 and 7?0μm, resp. This thin wetting layer leads to a new interpretation of the phase transition of H and Nb, involving the familiar long-range elastic interaction as well as a short-range surface free energy contribution.     

Intrinsic magnetostriction and phase transitions

A new possibility of first-order magnetic phase transitions in simple systems, based on the concept of intrinsic volume-magnetostriction Ω_s ≡ ? V_n/V_n, is suggested. The net volume V_n is defined as the difference between the total lattice volume and the sum of the individual atomic volumes. A magneto-volume equation of state for the net volume: Ω_s = Q₀η^s with s < 2, as well as the dependence of the effective exchange integral on the long-range order parameter η, are postulated. The value s ? 1.5 accounts well for the experimental values of the critical exponents β and δ, as well as for the deviation from linearity of the Arrott—Belov plots obtained for the ferromagnetic transition metals. The model leads to an order—order transition just below the order—disorder transition, thus providing an explanation for the two experimentally found temperatures, the forromagnetic Curie temperature and the paramagnetic Curie—Weiss temperature.     

Structural phase transitions in yttrium under ultrahigh pressures

X-ray diffraction studies were carried out on the rare earth metal yttrium up to 177?GPa in a diamond anvil cell at room temperature. Yttrium was compressed to 37% of its initial volume at the highest pressure. The rare earth crystal structure sequence hcp?→?Sm?type?→?dhcp?→?mixed(dhcp?+?fcc)?→?distorted fcc (dfcc) is observed in yttrium below 50?GPa. The dfcc (hR24) phase has been observed to persist in the pressure range of 50-95?GPa. A structural transition from dfcc to a low symmetry phase has been observed in yttrium at 99?±?4?GPa with a volume change of -?2.6%. This low symmetry phase has been identified as a monoclinic C2/m phase, which has also been observed in other rare earth elements under high pressures. The appearance of this low symmetry monoclinic phase in yttrium shows that its electronic structure under extreme conditions resembles that of heavy rare earth metals, with a significant increase in d-band character of the valence electrons and possibly some f-electron states near the Fermi level.     

Possibility of a distortion induced gap in intermediate valence compounds

It is shown that in some stoichiometric intermediate valence compounds a symmetry breaking distortion leading to a hybridization gap in the electronic density of states can exist. We study this possibility for the high pressure phase of SmS and the paramagnetic phase of TmSe.     

Jahn-Teller phase transitions; selection of the order parameter

A three-dimensional order parameter is proposed for Jahn-Teller phase transitions related to splitting of the ion E_g-level. A thermodynamic theory of these transitions is constructed on its basis. A selection rule of possible orderings is introduced that is based on the simultaneous entrance of the relevant order parameter into the composition of the mechanical and Jahn-Teller representations. Developed methods are approved for analysis of the structural transition in perovskites of the KCuF₃ type.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 12, pp. 51–55, December, 1989.