Charge transfer vibronic excitons: Charge-transfer lattice-instability effects

Two aspects for investigating bipolaronic excitons [charge transfer vibronic exciton (CTVE)] in ionic-covalent solids are considered. These aspects are predictions of the charge-transfer lattice instability corresponding to charge transfer and lattice anharmonicity, as well as to repulsion between different types of CTVEs in the order parameter field. Oxide crystals (SrTiO₃, BaTiO₃, K₃Na(CrO₄)₂) are considered as an example.     

Core electron excitation spectra of diamond,graphite, and glassy carbon

Low-energy electron energy loss spectra in theC(1s) core electron excitation region have been measured in diamond, graphite and glassy carbon in the non-differentiated form. The background subtractedN(E) spectrum has been proved to reflect the density-of-states (DOS) of the conduction band well, and the conduction band structures of these materials have been elucidated. The energy positions of the symmetry points in their conduction bands have been determined from the second-derivative spectra, which were obtained by numerical differentiation of the measuredN(E) spectra.     

Charge transfer excitons: dynamic theory of vibronic spectra

The vibronic spectra of charge transfer excitons (CTE) in a molecular one-component or alternatingly ordered two-component chain are treated in the framework of a dynamic approach (neglecting thermal excitations of the intramolecular vibrations). The model introduces two mechanisms of coupling between CTEs and vibrational quanta: (1) shift of the equilibrium positions of the nuclei in the ionized donor or acceptor; (2) change of the vibrational frequency in the ionized molecule. This model allows to generalize the simple CTE Hamiltonian and the vibronic Hamiltonian of Frenkel excitons. The linear optical susceptibility is calculated in the vibronic region (one CTE and one vibrational quantum). The double splitting of vibronics of CTEs was analyzed: (1) the splitting connected with the location of the intramolecular vibration on the donors or on the acceptors; (2) the splitting connected with the symmetry of the vibronic spectra (in the degenerate case). The general structure of the vibronic spectra of CTEs is established. It contains structureless absorption lines, which correspond to two-particle bands (the phonon is excited on a neutral molecule neighboring the donor or the acceptor) and Lorentz-type lines of one-particle states, which correspond to the bound propagation of the CTE and the phonon.     

Revised fine splitting of excitons in diamond

We study low-strain synthetic high pressure, high temperature diamonds by cathodoluminescence and observe novel fine structure in the free exciton and the boron-bound exciton emission. The basic spectral structure is a doublet with DeltaE approximately 11 meV common to both exciton spectra. This resolves the previously found inequivalence of free exciton ( approximately 7 meV) and bound exciton ( approximately 12 meV) fine splitting. It is argued that for a spin-orbit interaction Delta(0) much smaller than the excitonic binding ( E(X) approximately 80 meV) and the excitonic localization ( E(loc) approximately 51 meV) at the boron acceptor, the orbital momentum and the spin of the particles constituting the electron-hole pair are recoupled to form spin singlet and triplet exciton states as the elementary excitations.     

Electronic spectra and vibronic coupling of pyrazine

The absorption and fluorescence spectra of pyrazine have been observed in vapor, solution and crystal, and the vibrational structures have been analyzed in detail. The fluorescence spectrum consists of long progressions of the nontotally symmetric vibration ν₅(b_2g), and the absorption spectrum contains also the progression of the corresponding excited state vibration ν′₅(b_2g. However, the pattern of the latter progression is unusual because of the highly anharmonic nature of the potential of the ¹B^3u state, which may be expressed by a functional form containing a quadratic term in the normal coordinate. All the experimental results suggest that the known vibronic interaction between the ${}^1\text{B}{}_{\mathrm{3u}}\text{(n,π}{}^1\text{)}$ state and the ${}^1\text{B}{}_{\mathrm{1u}}\text{(π, π}{}^1\text{)}$ state through the vibration ν₂(b_2g) is strong. The vibronic coupling and the potential of the ¹B_3u state were found to be very sensitive to solvent.     

Core excitons in Ga-V compound semiconductors

The major chemical trends in the energies of Ga 3d core excitons in GaP, GaAs, and GaSb are accounted for by a theory which treats only the central-cell part of the electron-hole interaction.     

Configuration vibronic mixing for a neutral vacancy in silicon and diamond

Configuration vibronic mixing is considered for a fully symmetric Jahn-Teller electronic term with orientation-degenerate terms (due to the distortion direction) including a correlation correction in a single-open-shell approximation. The approach is nonempirical and involves only linear vibronic coupling. The adiabatic potential is a multiwell one, because the different configurations involved in the exact Jahn-Teller term have different vibronic coupling with a lattice distortion. The stabilization energy, the frequencies of local lattice vibrations, the vibronic coupling parameter, and the energy barriers to migration and to distortion-axis reorientation are estimated for a neutral vacancy in silicon and diamond with allowance made for configuration vibronic coupling. The estimates agree with the results obtained by different experimental and theoretical methods for a wide range of properties associated with the Jahn-Teller effect.     

Exchange coupling for excitons in quantum wires

We consider theoretically the exchange coupling for independent heavy excitons in both weakly and strongly confining quantum wires. We discuss different contributions for the spin depolarization in the presence of spin-conserving scatterings and show that localization effects weaken the spin depolarization rate.     

Isotope effects on vibronic coupling of pyrazine

The vibronic couplings of pyrazine-d₀ and pyrazine-d₄ between the lowest electronic excited states ¹B_3u(n, π^*) and ¹B_2u(π, π^*) through the out-of-plane CH bending vibration ν_10a(b_1g) have been studied from the Raman, electronic absorption and fluorescence spectra. The isotope effects on the scattering cross section of the ν_10a Raman line, the vibrational potential in the ¹B_3u(n, π^*) state and on the frequency change of the ν_10a vibration between the ground and the lowest electronic excited states are well explained by conventional Herzberg-Teller coupling mechanism. However, the intensities of the vibronic bands in the electronic absorption and fluorescence spectra are hardly explained with this coupling mechanism.     

Core excitons in the electronic polaron model

Summary The electronic polaron model of the exciton is used to study the dielectric response of a medium to the excitation of a ?core? level, by adopting the method of direct solution of the Eulerian functional variational equations. The dynamical response of the electronic polarization affects the electron-hole attraction and the exciton binding energy, in a way which depends on the basic parameters of the crystal (dielectric constant, effective masses, lattice parameter) through the core exciton radius and the polaron radius. When the former is much larger than the latter, static dielectric screening results. When the exciton radius is comparable to the polaron radius, the screening is reduced and the binding energy is increased. Core exciton binding energies are computed in a number of substances using the effective-mass approximation. Space dispersion of the dielectric function coupled to intervalley interaction may, however, contribute in some cases to reducing the excitonic radius and bringing about an instability to a deep state that would invalidate the effective-mass approximation. Based on work supported by the Italian Research Council (C.N.R.) through a contract G.N.S.M.     

Core hole,plasmon coupling in the soft X-ray appearance potential spectrum of graphite

A direct comparison is presented between the results of core-level characteristic loss and soft X-ray appearance potential spectroscopies for the case of K-shell excitation in graphite. The agreement between the results of these two techniques indicates that contrary to earlier suggestions, plasmon coupling to the suddenly created core hole during the excitation does not contribute appreciably to the spectral shape.     

Infrared luminescence and vibronic coupling in ZnTe:Fe2+

Samples of crystalline ZnTe with different concentrations of iron were prepared by the vertical high-pressure Bridgman method. Absorption and emission spectra were recorded at liquid-helium temperature in the region of the⁵ T ₂(D)⁵ E(D) infrared transitions of substitutional Fe²⁺(d ⁶) ions. In the range between 2400 and 2520 cm^–1 a rich structure is observed showing more lines than predicted by plain crystal-field theory. The explanation of all these lines is found after introducing a vibronic Jahn-Teller term to the Hamiltonian. A linear coupling between the doubly degenerate vibrational mode to the electronic orbitals of the ionic multiplet⁵ D is added to the electronic and vibrational terms of the Hamiltonian. A diagonalization follows using just one free parameter: the Jahn-Teller energy representing the strength of the coupling. The corresponding value is 3 cm^–1, which is identical to the one already reported for CdTe Fe²⁺. The calculated spectrum is in good agreement with the one determined experimentally. Measurements of the absorption spectra support conclusions drawn earlier about a Jahn-Teller coupling also for the excited multiplet. Finally a prediction of how the far-infrared would look like is also given.     

Wannier excitons signalling strong Coulomb coupling in graphene

The Wannier equation for quasiparticles with a linear dispersion is investigated. It is shown that Coulomb bound compounds of mass less electron-hole pairs can only exist if the effective coupling strength exceeds the critical value of approximately 0.46. At the critical value, a second-order transition to a weak Coulomb regime is found. It is shown that the existence of bound excitons indicates an instability of the noninteracting ground state.     

Coriolis coupling in degenerate vibronic states of spherical top molecules

The first-order contribution of coriolis coupling to the rotational energies of degenerate vibronic states of spherical top molecules is considered for both even and odd numbers of electrons in octahedral or tetrahedral molecules. For E vibronic states the contribution vanishes, while for F ₁, F ₂, E _1/2 and E _5/2 states simple formulae are given. For G _3/2 states the energies are in general complicated, but simple formulae are given for two limiting cases.     

Resonance Raman profile with consideration for quadratic vibronic coupling

A relation is found between the first-order Raman profile and the absorption spectrum of a scattering centre with regard to the quadratic vibronic coupling in a zero-temperature case. Two non-degenerate electronic states of the centre are considered, the adiabatic and Condon approximations are used, and the vibrations of the centre are assumed to be harmonic.     

New superhard carbon phases between graphite and diamond

Two new carbon allotropes (H-carbon and S-carbon) are proposed, as possible candidates for the intermediate superhard phases between graphite and diamond obtained in the process of cold compressing graphite, based on the results of first-principles calculations. Both H-carbon and S-carbon are more stable than previously proposed M-carbon and W-carbon and their bulk modulus are comparable to that of diamond. H-carbon is an indirect-band-gap semiconductor with a gap of 4.459 eV and S-carbon is a direct-band-gap semiconductor with a gap of 4.343 eV. The transition pressure from cold compressing graphite is 10.08 GPa and 5.93 GPa for H-carbon and S-carbon, respectively, which is in consistent with the recent experimental report.     

Strong coupling between localized plasmons and organic excitons in metal nanovoids

Hybrid emitting exciton-plasmonic composites are constructed by coating arrays of spherical nanovoids embedded in a gold film with organic semiconducting molecular J-aggregate films. In such plasmonic crystals, localized plasmons confined inside the voids can be excited. We report the first observation of polaritonic spectral narrowing and strong coupling between localized plasmons and J-aggregate excitons with Rabi splittings of 230 meV at room temperature.