The charge-transfer contribution to the intensity of hypersensitive trivalent lanthanide transitions

By considering the variation of charge-transfer energy and of the intensity parameters across isostructural series it is concluded that charge-transfer mixing is of negligible importance in accounting for the intensity of the hypersensitive transitions of the trivalent lanthanides. The experimental relationship between hypersensitive transition intensity and charge-transfer energy found for a particular member of the lanthanide series in various environments can be as satisfactorily explained by the ligand polarization theory as by charge-transfer mixing.     

Heavy-atom effect on radiative and radiationless transitions in charge-transfer complexes

The quantum yields of fluorescence and phosphorescence and decay times of fluorescence were measured for a series of charge-transfer complexes of hexamethylbenzene (an electron donor) with various electron acceptors containing heavy (halogen) atoms and the rate constants of different radiative and radiationless transitions were determined. It was found that radiative T₁ → S₀ transition, i.e. the phosphorescence, is strongly enhanced by the heavy-atom effect. The mechanism of the heavy-atom enhancement of charge-transfer phosphorescence is discussed and it is concluded that increasing spin- orbit mixing of radiative T₁ → S₀ charge-transfer transition with singlet-singlet, locally excited transition of acceptor molecule is responsible for the observed effects.     

Characterization of the two-photon absorption resonance that is due to the internal charge-transfer transition of a push pull molecule, 4-(diethylamino)-beta-nitrostyrene

The two-photon absorption resonance that is due to the internal charge-transfer transition of an organic push-pull molecule has been characterized. A nonlinear absorption spectrum of the 4-(diethylamino)- beta-nitrostyrene molecule was measured in a tetrahydrofuran solution by optical Kerr ellipsometry. The shape and the amplitude of the two-photon absorption spectrum are well described by a model that uses the relevant one-photon absorption spectrum related to the internal charge-transfer transition.     

Coherent control of charge and lattice dynamics in a photoinduced neutral-to-ionic transition of a charge-transfer compound

Coherent control of a charge-lattice coupled oscillation associated with the neutral (N)-ionic (I) transition was successfully demonstrated for a charge-transfer (CT) compound, tetrathiafulvalene-p-chloranil, with use of double femtosecond laser pulses. By changing the interval of the two laser pulses, amplitude of the oscillation in the reflectivity for the intramolecular transition band sensitive to the degree of CT was periodically changed. With increase of the pump intensity, the oscillation amplitude was dramatically enhanced. Such an enhancement is discussed in terms of the cooperative nature of the N-I transition.     

Competition between charge-transfer exciton dissociation and direct photocarrier generation in molecular donor-acceptor compounds

The interfacial charge-separation and photovoltaic characteristics of a molecular donor-acceptor charge-transfer compound were examined. Measurements of laser beam-induced currents on the single crystals allowed selective detection of hole and electron photocurrents through the metal-semiconductor interfaces. This method also reveals the exceptionally long diffusion length of 20 μm in the crystal. The transition from charge-transfer exciton dissociation to direct photocarrier generation is discussed on the basis of the photon-energy-dependent diffusion length and photon-to-current conversion spectrum.     

Vibronic charge-transfer excitons: Possible nature of the unusual properties of virtual perovskitelike ferroelectrics

A vibronic charge-transfer exciton, which is a pair of Jahn-Teller electron and hole polarons, is considered as a possible cause of the appearance of the Müller phase in the virtual ferroelectric SrTiO₃ and the “green” luminescence in the virtual ferroelectric KTaO₃. The two “green” luminescence bands can be associated with emission from two states of a typical intrinsic defect, viz., a vibronic charge-transfer exciton trapped by an oxygen vacancy and an isolated vibronic charge-transfer exciton. In both cases the “green” luminescence corresponds to the recombination of the electron and the hole in the vibronic charge-transfer exciton, which is accompanied by the emission of light. The properties of the Müller phase can be attributed to mixing of the normal state and states of the vibronic charge-transfer exciton phase when they interact with polarization in the soft SrTiO₃ matrix under the conditions of a pseudo-Jahn-Teller (pseudo-JT) effect on a soft TO mode of the displacement type. In this case the vibronic charge-transfer exciton phase forming the low-lying excited states has “order-disorder” degrees of freedom and exists at temperatures significantly below the point of the order-disorder ferroelectric transition in SrTiO₃ at T=T Q≈37 K. The corresponding lowering of the symmetry of the vibronic charge-transfer exciton phase to polar symmetry leads to the possibility of a long-period incommensurate phase in such excited states, which arises as a result of the appearance of a Lifshitz invariant. The valence-band state making the largest contribution of the pseudo-JT effect corresponds to a wave vector equal to the critical wave vector of the incommensurate vibronic charge-transfer exciton phase. When the temperature is lowered, the pseudo-JT distortion increases down to ∼T _Q and subsequently saturates in accordance with the saturation of the dielectric constant. The basic assumption in the model is that the temperature T=T _Q corresponds to the narrow temperature range for the transition from an intermediate to a strong pseudo-JT effect under the conditions for the realization of polarization tunneling states. The appearance of a significant admixture of states of the modulated ferroelectric vibronic charge-transfer exciton phase to the ground state under the conditions for the realization of polarization tunneling states at low temperatures provides an explanation for the principal properties of the Müller phase. Fiz. Tverd. Tela (St. Petersburg) 40, 907–909 (May 1998)     

The polarized charge-transfer spectrum of crystalline anthracene-TNB complex

The intermolecular charge-transfer spectrum of the crystalline anthracene-TNB complex has been measured, using polarized light. The crystal spectrum differs from that of the solution to a much greater degree than is the case for ordinary aromatic systems. The transition is polarized along the intermolecular axis and is blue-shifted with respect to the solution. There is pronounced vibrational structure, including a prominent 250 cm^-1 interval. A Davydov splitting of approximately 200 cm^-1 is observed, and this is shown to be in reasonable agreement with the known crystal structure and with the symmetry assignment of the transition, which is A′ ← A′ for the complex in solution and A ← A in the crystal.     

Crystal field splitting in correlated systems with negative charge-transfer gap

Special features of the crystal field splitting of d-levels in the transition metal compounds with small or negative charge-transfer gaps Δ(CT) are considered. We show that in this case the Coulomb term and the covalent contribution to the t(2g)-e(g) splitting have different signs. In order to check theoretical predictions we carried out ab initio band structure calculations for Cs(2)Au(2)Cl(6), in which the charge-transfer gap is negative, so that the d-electrons predominantly occupy low-lying bonding states. For these states the e(g)-levels lie below the t(2g) ones, which demonstrates that at least in this case the influence of the p-d covalency on the total value of the crystal field splitting is stronger than the Coulomb interaction (which would lead to the opposite level order). We also show that the states in the conduction band are made predominantly of p-states of ligands (Cl), with a small admixture of d-states of Au.     

Deactivation of an excited charge-transfer complex I. Influence of solvent polarity on radiative and radiationless transitions

The influence of solvent polarity on the fluorescence of charge-transfer complexes of pyromellitic dianhydride with some methylated benzenes has been investigated. Quantum yields and decay times of fluorescence, in mixed solvents of different polarities, have been measured. It was shown that with increasing solvent polarity the quantum yield of fluorescence is mainly decreasing owing to the decrease of the radiative transition probability k_f is due to the increasing degree of solvent-induced changes in the electronic and geometrical structure of the equilibrium excited state and increasing solvation of the components of the complex. Emissive properties of charge-transfer complexes are compared with emissive properties of heteroexcimers.     

Phase transition to the conducting state in a system of charge-transfer excitons at a donor-acceptor interface

We discuss the phase transition to the conducting state in a system of 2D charge-transfer excitons (CTEs) at a donor-acceptor interface. The phase transition arises due to strong dipole-dipole repulsion between CTEs which stimulates the population of free carriers in higher energy states even at low temperature. We use the computer simulations with the random distribution of excitons, with finite lifetime explicitly taken into account. The critical concentration of CTEs and their energy distribution are calculated. We also discuss the possibility of observing the predicted phenomena. Fiz. Tverd. Tela (St. Petersburg) 41, 781–784 (May 1999) Published in English in the original Russian journal. Reproduced here with stylistic changes by the Translation Editor.     

One-dimensional fluctuating nanodomains in the charge-transfer molecular system TTF-CA and their first-order crystallization

We report on the direct observation by x-ray diffuse scattering measurements of thermally induced one-dimensional nanoscale ordered fluctuations in the mixed-stack charge-transfer molecular system tetrathiafulvalene-p chloranil (TTF-CA), the prototype for the neutral-ionic phase transition. The unusual physical properties of this compound are considered to be driven by such one-dimensional excitations. The results are discussed in relation to previous experimental and theoretical experiments both at thermal equilibrium and under light irradiation.     

激发态电荷转移有机体的多铁性研究

随着人们对多铁性的深入了解,越来越多不同类型的有机多铁材料被合成出来.激发态电荷转移有机体的电荷转移网络是由一个提供电子的分子(给体donor,D~+)和一个接受电子的分子(受体acceptor,A~-)有序排列后构成的.D~+A~-长程有序排列,其激发态(激子)具有较长寿命和±1/2自旋,这是产生室温铁电性和铁磁性的根本原因.激发态容易受外场刺激,因此光照、磁场、电场、应力等能够很好地调控这类材料的铁电极化、磁矩和相应的磁电耦合系数.激发态电荷转移有机体不仅大大丰富了室温多铁材料体系,而且可以为开发新型多功能电子器件提供材料基础和技术储备.     

Flexible alteration of optical nonlinearities of iodine charge-transfer complexes in solutions

The type of donor used is found to influence greatly the optical nonlinearities of iodine charge-transfer (CT) complexes in solutions for several solvents. The magnitude and sign changes of nonlinear absorption of iodine CT complexes for different solvents as donors are observed, which implies the transition from saturable absorption to reverse saturable absorption. Compared with C60 in toluene, iodine CT complexes with toluene and benzene demonstrate larger reverse saturable absorption. Meanwhile, flexible alteration of optical nonlinearities is easily obtained by adjusting the mixture ratio of different solvents, yielding a prospective means of constructing a nonlinear medium with a large nonlinear coefficient.     

Spectro-streak picosecond studies of intramolecular charge-transfer fluorescence

A spectro-streak photometer, an instrument for simultaneously measuring fluorescence intensity, time, and wavelength,I(t, ), with a single picosecond excitation pulse, has been constructed. Two typical and currently highly topical examples of mesurements are discussed. (1) the temporal development of the fluorescence form the intramolecular charge-transfer (ICT) state of the rigid aromatic compound 4,5-(1-methylindolino)3,4-naphthanthracene is studied in the protic solvent hexanol. (2) Propyl chain-linked pyrene/N,N-dimethylaniline is used as the model compound to study conformational changes associated with the transition from a contact ion pair to a sandwich exciplex.     

Phonon bands in a π-electron charge-transfer complex

Phonon bands in mixed-stack π-electron charge-transfer complexes are investigated using Raman spectroscopy. Specifically, the Raman phonon spectra of naphthalene: antimony trichloride system is discussed in detail. The effect of the substitution of the donor and the acceptor is used to examine relative amplitudes of various motions on the donor and the acceptor. Phonon delocalization is investigated using various mixed crystals containing donor and acceptor impurities. The result obtained is discussed in terms of two models: (i) the giant molecule model, and (ii) the sublattice model.     

Induced-charge errors in charge-transfer measurement

Induced-charge errors cause a degree of under-recording when charge-transfer measurements made with high-speed, unshielded test-probes are used for assessing electrostatic hazards. Published information does not quantify the errors well enough to allow appropriate test tolerances to be set. This work tries to rectify that situation by calculating the collection-efficiency (ratio of measured to actual charge-transfer) for sparks and brush discharges to earthed spherical probes from representative flat or convex test bodies. Our results include data on the worst-case induced-charge errors for charge-transfers of 60 nC, 30 nC and 10 nC, which have been suggested as hazard thresholds for Gas Group IIa, IIb and IIc materials respectively. For 60 nC charge-transfers from non-concave surfaces, our data indicate that the possible under-recording of charge-transfers measured with fast, unshielded probes can be dealt with by applying a correction factor of ×2 to ×2.5. For 30 nC and 10 nC charge-transfers, or for discharges from concave surfaces, the necessary correction is both larger and more sensitive to gap geometry. Consequently, we do not recommend the use of fast, unshielded probes for assessing the electrostatic hazards arising from charges on concave surfaces or with materials that are more sensitive to ignition than those in Gas Group IIa.     

Similarities in electronic properties of organic charge-transfer solids and layered cobaltates

The apparently counterintuitive carrier concentration-dependent electronic properties of layered cobaltates have attracted wide interest. Here we point out that very similar carrier-concentration dependence has previously been noted in strongly correlated quasi-one dimensional (quasi-1D) organic charge-transfer solids. The normal states of both families can be understood, over the entire range of carrier concentration of interest, within the extended Hubbard Hamiltonian with significant intersite Coulomb interaction. As with the charge-transfer solids, superconductivity in the cobaltates appears to be limited to bandfilling of one-quarter. We point out further that there exist other families of correlated superconductors, such as spinels, where too strong correlations, geometric lattice frustration and bandfilling of one-quarter seem to be the essential features of the unconventional superconductors.     

NiO: correlated band structure of a charge-transfer insulator

The band structure of the prototypical charge-transfer insulator NiO is computed by using a combination of an ab initio band structure method and the dynamical mean-field theory with a quantum Monte-Carlo impurity solver. Employing a Hamiltonian which includes both Ni d and O p orbitals we find excellent agreement with the energy bands determined from angle-resolved photoemission spectroscopy. This brings an important progress in a long-standing problem of solid-state theory. Most notably we obtain the low-energy Zhang-Rice bands with strongly k-dependent orbital character discussed previously in the context of low-energy model theories.     

Tuning interfacial charge-transfer excitons at polymer-polymer heterojunctions under hydrostatic pressure

We present photoluminescence spectroscopy of blend thin films of poly(9,9-di-n-octylfluorene-alt-benzothiadiazole) (F8BT) with electron-donating copolymers under hydrostatic pressure. The photoluminescence spectrum of F8BT redshifts by 530+/-60 meV over pressures of 0.1 MPa-8.8 GPa. That of the interfacial charge-transfer exciton redshifts by 270-370 meV over a similar pressure range. Despite the relatively small shift of the charge-transfer exciton, the excited state dynamics at the molecular heterojunction are strongly enhanced due to the decreasing intermolecular distance, leading to favored exciplex emission.     

The effect of bromine substitution on the charge-transfer emission of the complex of phenanthrene and tetracyanobenzene

The absorption spectra of the charge-transfer complexes of sym-tetracyanobenzene (TCNB) with phenanthrene, 9-bromophenanthrene, and 9,10-dibromophenanthrene are measured in chloroform solutions at room temperature. The total emission and phosphorescence spectra of the donors and the complexes are measured at 77 K in rigid glasses. The phosphorescence decay lifetimes are determined for phenanthrene, TCNB, and for the phenanthrene-TCNB complex, and a decrease in the phenanthrene-TCNB complex lifetime relative to the lifetimes of the two components is observed. The luminescence spectra of the complexes exhibit both a red shift and a lack of structure as compared with the donor spectra. The results are interpreted, in agreement with the results of Iwata et al. for the phenanthrene-TCNB complex (1), as an indication that there is a considerable degree of charge-transfer character in the lowest triplet state (T₁). Bromine substitution leads to a decrease in the energy of the phenanthrene triplet state. As a result, the energy gap between the donor molecule triplet state and the complex charge-transfer triplet state decreases from phenanthrene, to 9-bromophenanthrene, to 9,10-dibromophenanthrene. The results suggest that the proximity of these two triplet states in 9,10-dibromophenanthrene and its charge-transfer complex leads to some local donor triplet state character in the emitting complex triplet state.