Ultrafast relaxation in quasi-one-dimensional organic molecular crystals

We present a comprehensive study of ultrafast relaxation properties of optical excitations in thin films of quasi-1D stacked organic materials PTCDA (3,4,9,10-perylenetetracarboxylic dianhydride) and MePTCDI (N,N'-dimethylperylene-3,4,9,10-dicarboximide) over five decades of time. Pump-probe experiments reveal excitonic intraband relaxation time constants of 65 fs for MePTCDI and 100 fs for PTCDA. The initial time-resolved luminescence anisotropy is consistent with the exciton model of Davydov-split states. The subsequent decay of the anisotropy can be explained with a thermally activated exciton hopping process. A full understanding of the pump-probe experiments calls for an explanation beyond the models presently available.     

Optical properties of quasi-one-dimensional molecular crystals with different polarizations

Quasi-one-dimensional organic compounds in which the acceptor TCNQ molecules form dimers are studied. Site Orbitals describing the electron in half of the TCNQ molecule are introduced. Hubbard's model is generalized so as to take into account the Coulomb repulsion between two electrons at one site. It is shown that the optical excitations of the electron are asssociated with intramolecular vibrations both when the incident light is polarized along the TCNQ chains and when the incident radiation is polarized transverse to the chains. The conductivity of the system with different polarizations is calculated taking into account the electron-vibrational interaction.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 2, pp. 74–78, February, 1986.     

Coherent phonons and their properties

The optical phonons in semimetals, semiconductors, and superconductors were studied by the light reflection techniques with femtosecond time resolution and by the method of spontaneous Raman scattering. During measurements in the time domain, the phonon system is converted into a coherent state by the first ultrashort laser pulse and then probed at a variable delay by the second pulse. In this case, the phonons are shown to occur in a nonclassical state in which their fluctuational properties, different in various quadratures, are described by periodic functions of time. A comparison of the results obtained in the time and frequency domains gives evidence that the energies of thermal and coherent phonons coincide, while their dephasing and energy relaxation times are different.     

Singlet triplet-triplet-triexcitons in organic molecular crystals

A theory on the formation of triexcitons consisting of one singlet exciton and two triplet excitons is developed by considering exciton-exciton dynamical interactions. The conditions for the existence of the singlet-triplet-triplet-triexciton bound states are established and discussed.     

Coherent phonons and excitons in biological systems

The possibility of Bose condensation of phonons in biological systems induced by millimeter electromagnetic waves is discussed. The existence of bistability and hysteresis is predicted and the possibility of Bose condensation of excitons, the creation of solitons and superfluid transfer of energy in such systems is also discussed.     

Coherent backscattering in nematic liquid crystals in an external magnetic field

We consider multiple light scattering in a nematic liquid crystal. Using the Monte Carlo method, we calculate for the first time the effect of a magnetic field on the shape of the peak of coherent backscattering taking into account the long-range action of fluctuations of the orientational order and anisotropy of the scattering length. For a small number of initial and final scattering events, we take into account the ordinary mode of light, which is weakly scattered in a nematic liquid crystal (NLC), whereas a strongly scattered extraordinary mode is taken into account for all scattering events. For simplicity, we use a single-constant approximation of the NLC elastic moduli. We show that the angular shape of the peak of coherent backscattering remains nearly unchanged, whereas the magnetic field and the scattering phase function vary by several orders of magnitude.     

Polarization in organic molecular crystals and charge-transfer salts

Polarization in insulators is a general phenomenon that extends over nanometer distances. Two special cases illustrate recent theoretical progress. Polarization energies of localized charges in organic molecular crystals exceed the bandwidth and redistribute the charge density. A systematic treatment of electronic polarization is summarized in the limit of zero intermolecular overlap for pentacene crystals or thin films on metallic substrates, with special attention to the transport gap for producing a separated electron–hole pair and the optical dielectric tensor of the crystal. When overlap cannot be neglected, the general formulation of polarization in extended insulators is in terms of the exact ground state's phase. This formulation is applied to organic charge-transfer (CT) salts whose correlated electronic structure is described by one-dimensional Peierls–Hubbard models. Near the Peierls instability, coupling to lattice modes generates large peaks in the dielectric response that is primarily due to lattice vibrations. Comparisons with experiment are mentioned for both organic molecular crystals and CT salts.     

Incoherent singlet-triplet biexcitons in organic molecular crystals

The conditions of the existence, the energy spectrum of internal motion and the dynamics of propagation as a whole of incoherent singlet-triplet biexcitons in organic molecular crystals is studied theoretically. It is assumed that the group velocity of the propagation of singlet excitons is very high with respect to that of triplet excitons.     

Charged Frenkel biexcitons in organic molecular crystals

It is known that the energy of the lowest electronic transition in the neutral molecules of anthracene, tetracene, and other polyacenes is blue-shifted in comparison with the corresponding transition energy in univalent molecular ions. This effect in a molecular crystal may be responsible for the attraction between a molecular (Frenkel) exciton and a charge carrier. Due to this attraction, a bound state of Frenkel exciton and free charge (charged Frenkel exciton) may be formed [5]. As we demonstrate below, the same mechanism can be responsible for the formation of a charged biexciton (bound state of two Frenkel excitons and a charge carrier). A one-dimensional lattice model is used which corresponds to J aggregates and is also a good approximation for quasi-one-dimensional crystals. Calculations are performed for molecular crystals like tetracene, where the exciton band at low temperature is much narrower than the band of the charge carrier.     

The interaction of excitons in the superliquid state with phonons in molecular crystals

The energy spectrum of excitons in the superliquid state has been investigated in interaction with phonons in molecular crystals. The corresponding branches of the energy spectrum of elementary excitations have been determined and the effect of the interaction with phonons on their stability has been investigated and discussed. The possibility of the resonance excitation of hydrons by means of phonons is discussed.     

Electronic correlations in oligo-acene and -thiopene organic molecular crystals

From first-principles calculations we determine the Coulomb interaction between two holes on oligo-acene and -thiophene molecules in a crystal, as a function of the oligomer length. The electronic polarization of the molecules that surround the charged oligomer reduces the bare Coulomb repulsion between the holes by approximately a factor of 2. The effects of relaxing the molecular geometry in the presence of holes is found to be significantly smaller. In all cases the effective hole-hole repulsion is much larger than the valence bandwidth, which implies that at high doping levels the properties of these organic semiconductors are determined by electron-electron correlations.     

Electron localization in quasi-one-dimensional organic conductors

The theory of electron localization in quasi-one-dimensional organic conductors is reviewed in detail. The effective diagram technique to take into account strong scattering and commensurability effects is developed using the Berezinsky method. The singularities of the electron density of states, of the localization length and of the static dielectric constant near the middle of the electron band and near other rational points of the band are discussed. A transition similar to the Anderson transition is found near the band edge. The effects of the electron-phonon interaction are taken into account and exact results for the hopping conductivity are obtained. The experimental data on the electrical and optical properties of TCNQ salts with strong structural disorder and of other quasi-1d organic conductors are reviewed and analysed.     

Nonradiative heterofusion of excitons in doped organic molecular crystals

The nonradiative heterofusion of a host exciton with a guest molecule electronic excitation resulting in a higher electronic neutral single excited state is examined theoretically in the doped organic molecular crystals. The heterofusion process is treated as a nonradiative spontaneous multi-lattice phonon transition of the crystal from the electronic double excited initial state to the electronic single excited final state under the action of the interaction between the host molecules and the guest molecule. Two heterofusion channels are considered: the first one resulting in a higher electronic excited state of the guest molecule and the second one resulting in a higher host exciton state. The corresponding rate constants are calculated and discussed within the framework of the first order time dependent perturbation theory.     

Origin of temperature-independent electron mobilities in organic molecular crystals

Recently the almost-temperature-independent mobility was observed for electrons in anthracene, naphthalene, and As₂S₃ in the direction with a narrow bandwidth. It is attributed to the phonon-induced electron hopping between planes along which the electron motion is coherent in a two dimensional energy band. The mobility increases abruptly below about the Debye temperature due to the increasing contribution of the electron transfer without phonon participation, as observed in naphthalene.     

Self-energy of phonons in anharmonic one-dimensional crystals

Using the expression obtained by Green's function methods the self-energy of phonons, interacting through anharmonic terms of third and fourth order in the expansion of the potential energy, is calculated for a linear chain without further approximations. The phonon energy shift and width show strong dependence on the frequency and the wave-vector.     

Transformation of charge transfer excitons into molecular excitons in molecular organic crystals

Formulae for persec probabilities of the nonradiative and radiative transformation of charge transfer excitons into molecular excitons in molecular organic crystals are derived and discussed. Numerical calculations are performed for solid naphtalene and anthracene.     

Raman phonons in multiferroic FeVO_4 crystals

Multiferroic materials are promising candidates for next-generation multi-functional devices, because of the coexistence of multi-orders and the coupling between the orders. FeVO4 has been confirmed to be a multiferroic compound,since it exhibits both ferroelectricity and antiferromagnetic ordering at low temperatures. In this paper, we have performed careful Raman scattering measurements on high-quality Fe VO4 single crystals. The compound has a very rich phonon structure due to its low crystal symmetry(P- 1) and at least 47 Raman-active phonon modes have been resolved in the low and hightemperature spectra. Most of the observed modes are well assigned with aid of first-principles calculations and symmetry analysis. The present study provides an experimental basis for exploring spin-lattice coupling and the mechanism of multiferroicity in FeVO4     

Long wavelength optical phonons in mixed crystals

Experimental data on optical phonons in mixed crystal systems obtained by infra-red, Raman, and other optical measurements are reviewed. In terms of their spectral behaviour, mixed crystals may be classified into different types, using as criteria the mass ratios of the constituent atoms and the inter-atomic forces. Several phenomenological models have so far been proposed for the explanation of the mixed crystal behaviour; these are reviewed. The difficulties facing a realistic and thorough lattice dynamical calculation of a disordered system are pointed out. Further experimental work needed for confirming and gaining understanding of the true behaviour types of some mixed crystal systems is suggested.