Nature of the magnetic excitation spectrum in (Sm,Y)S: CEF effects or an exciton?

The dynamic magnetic susceptibility spectrum in a single-crystal sample of the intermediate-valence compound Sm_0.67Y_0.33S is studied by inelastic neutron scattering with neutron momentum transfer and sample temperatures varying over wide ranges. Two coupled collective modes have been found in the spectrum. Unlike the higher energy mode, whose intensity approximately follows the form factor of Sm²⁺, the lower energy mode exhibits a stronger angular dependence than could be expected from the form factor for the localized f electrons. The total intensity of the inelastic component of the magnetic response decreases with increasing temperature; this is accompanied by the appearance of a broad quasi-elastic signal of a magnetic nature at significantly lower temperatures than follows from the calculated intensities of the transitions within the excited multiplet of the Sm²⁺ ion. An analysis of the observed features allows the suggestion to be made that the fine structure of the magnetic excitation spectrum in (Sm,Y)S is associated with the formation of an exciton-like intermediate-valence state on Sm ions rather than with the crystal-electric-field effects.     

Resonant scattering and optical properties of intermediate valence Sm1−xYxS

The intermediate-valence state of Sm in Sm_1?xY_xS has been investigated in terms of the d.c. and optical scattering time of the conduction electrons. Strong resonant scattering in the collapsed metallic phase is attributed to the pinning of the Fermi level E_F within a mixed-configuration resonant state. The composition- and temperature dependent electronic phase transition is found to occur when E_F reaches the resonant state.     

Electrical and magnetic properties of CeNi4In with Ce in saturated valence state

Measurements of the electrical resistance, thermopower, and magnetic susceptibility of CeNi₄In have been carried out within the 4.2–400 K range, with Ce in saturated valence state. It is shown that this state of Ce in metallic compounds is characterized by formation of a fine structure in the density of states near the Fermi level, which is qualitatively different from the case of usual intermediate-valence state. Fiz. Tverd. Tela (St. Petersburg) 40, 7–9 (January 1998)     

Manifestation of valence change in Ce1-xScxAl2 by neutron scattering

Neutron-scattering experiments demonstrate that the Ce-ions in Ce_1-xSc_xAl₂ are trivalent up to x = 0.4, undergo a change into an intermediate-valence state between x=0.4 and 0.5, and show, upon further increasing x, a continuous increase of valence, eventually reaching a completely demagnetized state of Ce for dilute (Ce,$\text{Sc}$)Al₂ alloys.     

Crystal field in valence-fluctuating CeNi-based compounds

The effects of the crystal field (CF) on the paramagnetic Pr ion in a number of compounds of the type R_1−x Pr_xNi (R = Ce, La, Y), in which a transition of the cerium ions from an intermediate-valence into a Kondo state occurs as La is substituted for Ce, are investigated. The level schemes of the Pr ion in the CF are reconstructed from inelastic neutron scattering spectra and the temperature dependence of the heat capacity in different magnetic fields (B=0–8 T). The parameters of the low-symmetry CF in the compounds RNi are determined from the experimental data. It is established that in the Kondo regime the hybridization of the f electrons with conduction electrons only gives a proportional increase in all the parameters of the CF potential. At the same time, partial delocalization of the f electrons in the intermediate-valence state results in charge redistribution, which is manifested in different scales for the changes in the different CF parameters. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 12, 947–952 (25 June 1996)     

Resonance-Raman-induced Kerr effect in molecules in the ground and electronically excited states

A theoretical investigation of the resonantly enhanced, Raman-induced Kerr effect (resonance-RIKE) is given, taking into account the resonance absorption of the laser wave and the population of excited electronic states. Line shape, maximum amplification and optimum conditions for the resonance-RIKE from the ground state as well as for the resonance-RIKE from an initial excited electronic state are discussed in detail. The possibility is studied of applying this method to the investigation of the vibrational structure of excited electronic states in molecules.     

Electronic structure and molecular spectroscopic constants of ScN and ScP investigated by several quantum chemistry methods

The electronic structure of the ScN and ScP molecules is a subject of controversy and turns out to be a challenging problem in quantum chemistry. We show that the ground-state electronic structure for both molecules depends critically on the choice of methods used which incorporate different ways of accounting for electron correlation. A parallel ab initio, DFT and TD-DFT study is performed for this purpose and uses sufficiently flexible basis sets able to reproduce accurate electronic structures, as well as correct spectroscopic constants.

In the ab initio methodology, results have been obtained with methods such as Hartree-Fock (HF), M?ller-Plesset perturbation theory (MPn), direct configuration interaction (CI), quadratic configuration interaction (QC), coupled cluster configuration interaction (CC), complete active space self-consistent field (CASSCF) and multireference configuration interaction (CIPSI) methods. In the DFT methodology, various ‘pure’ and ‘hybrid’ density functionals are used and the corresponding results are compared to sophisticated ab initio methods and to available experimental data.

All the methods used show that the ground state of both molecules is ¹Σ⁺, but two electronic structure natures, ¹Σ⁺ open-shell or ¹Σ⁺ closed-shell, are competitive and depend on the method employed. All the ab initio methods based on a single determinant wavefunction suffer seriously in predicting clearly the exact nature of the ground state or its correct structural and spectroscopic parameters. However, the ab initio methods based on a multiconfigurational wavefunction appear to be successful in describing correctly, within one shot, the electronic structure and the molecular spectroscopic constants. The ground state, particularly for the ScN molecule, presents an unusual electronic structure: the presence of degenerate determinants, quasidegeneracy with other states and one avoided crossing in the region around the equilibrium distances. The bonding of the ground state is a two open-shell ¹Σ⁺ state described as a π double bond and a Σ dative bond; the real triple bond ¹Σ⁺ state, i.e. closed-shell state, is found to lie higher in energy. The potential energy curves of the lowlying electronic states, the derived electronic structures and various molecular spectroscopic constants are presented and discussed for each method employed.     

The single-determinant approximation with a local potential for excited states

The specific features of the calculations of the electronic structure in the approximation of a local exchange potential that is identical for all the electrons involved are considered. An optimized effective potential method is proposed for calculating the energies of excited electronic states of the same symmetry. A single-particle Schrö dinger equation is derived for an excited state whose orbitals are described by a single-determinant wave function orthogonal to the ground state. The equations determining the local potential for excited states are obtained within the variational approach. The solution to these equations is analyzed in the framework of the parameterized representation of the effective potential. The efficiency of the proposed method is demonstrated by calculating the energies of three excited states of the same symmetry for a HeH molecule. The difference between the results obtained by the Hartree-Fock method and the method proposed in this paper is equal, on average, to 0.05%. A comparison with the results obtained from precise calculations based on the configuration interaction method shows that the accuracy in determining the energy of the excited states by the optimized effective potential method is comparable to the accuracy in calculating the energy of the ground state.     

Geometry Relaxation of Photoexcited States in Conjugated Molecules

The random phase approximation combined with semiempirical Hamiltonians is applied to compute and analyze electronic structure and excited state adiabatic potentials of several conjugated molecules. Calculated excited state energies and parameters of molecular adiabatic surfaces characterize the coupled dynamics of vibrational and electronic degrees of freedom. The analysis identifies the specific torsional and bond-stretching nuclear motions that dominate the excited state relaxation and lead to self-localized excitations. This approach is an inexpensive and numerically efficient method of computing molecular excited state adiabatic surfaces and modeling femto-to-pico second time-dependent photoexcitation processes along chosen trajectories.     

The equivalent potential of water molecules for electronic structure of alanine

Using ab initio calculations based on density functional theory, an equivalent potential of water molecules for the electronic structure of Ala in solution has been obtained. The calculation process consists of three steps: first, the geometric structure of Ala + nH₂O system is determined by searching for the lowest energy of the system using free cluster calculation method. Second, based on the geometric structure obtained, the electronic structure of Ala with the potential of water molecules is calculated using a self-consistent cluster-embedding method. Finally, after replacing water molecules with dipoles, the electronic structure of Ala with the potential of dipoles is calculated. The dipoles are adjusted so the electronic structure of Ala with the potential of dipoles is close to that of water molecules. The calculated results show that the main effect of water molecules is to raise the state for methyl CH₃ by about 0.14 Ry, raising all other eigenvalues by about 0.059 Ry, and widening the energy gap by about 25%. In contrast, the replacement of water molecules by dipoles is comparatively efficient, showing that the effect of water molecules on the electronic structure of Ala can be simulated by a dipole potential, which would be a shortcut calculation.     

不同位置取代的三氰基乙烯基蒽的含时密度泛函研究

运用密度泛函理论(DFT)RB3LYP方法和ab initio HF单激发态相互作用(CIS)法分别优化了2-三氰基乙烯基蒽(2-TCVA)和9-三氰基乙烯基蒽(9-TCVA)分子的基态及最低激发单重态几何结构.系统分析了前线分子轨道特征,并探索了电子跃迁机理.应用含时密度泛函理论计算了分子的电子光谱,计算结果与实验值符合得较好.     

The Electronic and Lattice Structures of the Groundand the Polaron States of Polymer Poly (Phenylene Vinylene) (PPV)

The electronic and lattice structures of poly (phenylene vinylene) (PPV) are studied theoretically. Both the electron-electron and electron-phonon interactions are taken into account in the Pariser-Parr-Pople model. The electronic band and the lattice structure of the ground state and the polaronic state are calculated by means of the unrestricted Hartree-Fock method. In the ground state, there exist eight bands in PPV including four valence bands and four conduction bands, and the benzenes can be considered to be rigid. The polaron induces the split of energy bands. There are four localized electronic states within the energy gap. The defect of the polaron appears to extend over about 5 units. The benzenes are strongly affected by the electron-phonon interaction. Our calculation for the energy band structure of the ground and polaron states are consistent with experimental absorption spectra. The results of our calculation show that the electron-phonon and inter-site electron-electron interactions play an important role in determining the electronic and lattice structures.     

The Electronic and Lattice Structures of the Ground and the Polaron States of Polymer Poly (Phenylene Vinylene) (PPV)

The electronic and lattice structures of poly (phenylene vinylene) (PPV) are studied theoretically. Both the electron-electron and electron-phonon interactions are taken into account in the Pariser-Parr-Pople model. The electronic band and the lattice structure of the ground state and the polaronic state are calculated by means of the unrestricted Hartree-Fock method. In the ground state, there exist eight bands in PPV including four valence bands and four conduction bands, and the benzenes can be considered to be rigid. The polaron induces the split of energy bands. There are four localized electronic states within the energy gap. The defect of the polaron appears to extend over about 5 units. The benzenes are strongly affected by the electron-phonon interaction. Our calculation for the energy band structure of the ground and polaron states are consistent with experimental absorption spectra. The results of our calculation show that the electron-phonon and inter-site electron-electron interactions play an important role in determining the electronic and lattice structures.     

Spectroscopy of low and intermediate Z elements at extreme conditions: in situ studies of Earth materials at pressure and temperature via X-ray Raman scattering

ABSTRACT

X-ray Raman scattering spectroscopy is an emerging method in the study of low and intermediate Z elements' core-electron excitations at extreme conditions in order to reveal information on local structure and electronic state of matter in situ. We discuss the capabilities of this method to address questions in Earth materials' science and demonstrate its sensitivity to detect changes in the oxidation state, electronic structure, coordination, and spin state. Examples are presented for the study of the oxygen K-, silicon L- and iron M-edges. We assess the application of both temperature and pressure in such investigations exploiting diamond anvil cells in combination with resistive or laser heating which is required to achieve realistic conditions of the Earth's crust, mantle, and core.     

Anomalous electrodynamic response in the mixed-valence superconductor CeRu2

We report the first results of microwave magnetoabsorption measurements (35–140 GHz) in the intermediate-valence superconductor CeRu₂. The anomalous electrodynamic response is found to derive from a transition from a weak to a strong pinning regime in the superconducting mixed state of this unusual metal. The experimental results strongly support the appearance in the CeRu₂ mixed state of a first-order phase transition that may be explained in terms of Fulde-Ferrel-Larkin-Ovchinnikov state formation. Pis’ma Zh. éksp. Teor. Fiz. 69, No. 10, 745–749 (25 May 1999) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Magnetism and electronic structure of Mn- and V-doped zinc blende ZnTe from first-principles calculations

By means of the first-principles full potential linearized augmented plane-wave method within the local density approximation for the exchange-correlation functional, we have investigated the magnetism and electronic structure of Mn- and V-doped zinc blende ZnTe. Total energy calculations show that, for high doping concentration (12.5%), ZnTe:Mn has an antiferromagnetic ground state while the ferromagnetic state is more favorable than the antiferromagnetic state for ZnTe:V. Furthermore, ZnTe with a low doping of Mn (6.25%) has a stable ferromagnetic ground state, which is in agreement with the experimental results. The calculated magnetic moment of ZnTe doped with Mn (V) mainly originates from transition metal Mn (V) atom with a little contribution from Te atom due to the hybridization between Mn (V) 3d and Te 5p electrons. Electronic structure indicates that Mn-doped ZnTe is a semiconductor, but V-doped ZnTe shows a half-metallic characteristic. We also discuss the difference between electronic and magnetic properties for ZnTe doped with 12.5% and 6.25% Mn.     

The self-consistent electronic structure of rectangular free-standing quantum wires: Fourier expansion approach

A method for the self-consistent calculation of rectangular free-standing quantum wires is presented. The method is also used for the electronic structure calculation of cladded quantum wires. It relies on the wavefunction's Fourier expansion, and uses the structure symmetry to save computation time. Calculations are performed for these two types of quantum wire at a number of dopant and surface state densities, and the influence of various parameters is analyzed. At low temperatures, the occurrence of Friedel oscillations is noticed, arising from a very limited number of well separated electronic states.     

Multiple intermediate valence in plutonium

On the basis of the concepts of an intermediate-valence (IV) regime, an empirical model is proposed that quantitatively describes the magnetic susceptibility, specific heat, and effective atomic volume of the low-temperature α phase and the gallium or aluminum-stabilized face-centered cubic (fcc) δ phase of plutonium metal. The results of the paper allow one to estimate the entropy change associated with the α → δ structural phase transition, the value of this change being very close to the experimental value. According to the model, both phases of plutonium are systems with multiple intermediate valence, whose ground state is a many-particle Kondo singlet, and fluctuations occur between 5f electron configurations with integer valences of 3+, 4+, and 2+.     

Influence of the substrate properties on the electronic structure of organic film-inorganic substrate interfaces

The structure of electronic states at the interfaces between perylene tetracarboxyldianhydride films and ZnO, Cu, GaAs, and InAs substrates is studied by the method of total current spectroscopy. It is found that the physicochemical properties of the substrate have a strong effect on the electronic state configuration in the substrate and film. On the basis of the experimental data, potential diagrams of the interfaces are constructed, which illustrate the formation of sharp and extended dipole layers, change in the charge state of surface levels, and modification of the electronic structure of the film.     

Electronic structure of Chevrel Phases: Emphasis on the part played by the cluster twisting angle through a LCAO-EHT tight binding study

The electronic structure of PbMo₆S₈ has been investigated using the so-called EHT-tight-binding method. An idealized cubic and an experimental distorted geometry are used, with standard atomic orbital parameters and diagonal H-matrix elements. A full band structure is presented in the idealized case. In both cases, the density of state curves computed using an integration over the Brillouin zone are also presented. The results show the importance of the twisting angle on the electronic structure near the Fermi level.