Geometry and quadratic nonlinearity of charge transfer complexes in solution: a theoretical study

In this paper, we have computed the quadratic nonlinear optical (NLO) properties of a class of weak charge transfer (CT) complexes. These weak complexes are formed when the methyl substituted benzenes (donors) are added to strong acceptors like chloranil (CHL) or di-chloro-di-cyano benzoquinone (DDQ) in chloroform or in dichloromethane. The formation of such complexes is manifested by the presence of a broad absorption maximum in the visible range of the spectrum where neither the donor nor the acceptor absorbs. The appearance of this visible band is due to CT interactions, which result in strong NLO responses. We have employed the semiempirical intermediate neglect of differential overlap (INDO∕S) Hamiltonian to calculate the energy levels of these CT complexes using single and double configuration interaction (SDCI). The solvent effects are taken into account by using the self-consistent reaction field (SCRF) scheme. The geometry of the complex is obtained by exploring different relative molecular geometries by rotating the acceptor with respect to the fixed donor about three different axes. The theoretical geometry that best fits the experimental energy gaps, β(HRS) and macroscopic depolarization ratios is taken to be the most probable geometry of the complex. Our studies show that the most probable geometry of these complexes in solution is the parallel displaced structure with a significant twist in some cases.     

Study of the pair correlations between p-nitroaniline molecules in solution by depolarized hyper-Rayleigh scattering

The concentration dependence of the hyper-Rayleigh scattering depolarization ratios of p-nitroaniline in solution was obtained and the results were compared with theory. It was found that the experimental data can be theoretically accounted for by using a pair distribution function that includes only direct correlation, with the molecules interact through a dipolar hard-sphere potential. The results show that short-range dipole-dipole interactions are responsible for the correlation between pairs of p-nitroaniline molecules in solution.     

Study of intermolecular interactions in liquid nitrobenzene by depolarized hyper-Rayleigh scattering

We employed depolarized hyper-Rayleigh scattering (HRS) to investigate the intermolecular interactions in liquid nitrobenzene. By comparing the depolarization ratios of the second-harmonic scattered light from neat nitrobenzene and mixtures of nitrobenzene and methanol of varying mixing ratios, we demonstrated the existence of a coherent component of HRS in liquid nitrobenzene. The coherent component was found to essentially disappear at a sufficiently high dilution of the nitrobenzene liquid. We also observed that both localized orientational correlation and delocalized libron excitation contribute to coherent HRS in liquid nitrobenzene. The delocalized contribution to coherent HRS was found to diminish much more readily with the introduction of interstitial foreign molecules than the localized contribution.     

Chemical applications of hyper-Rayleigh scattering in solution

Hyper-Rayleigh or second harmonic Rayleigh scattering (HRS or SHLS) has been employed to measure equilibrium physical properties of molecules in solution. It has been utilized in our laboratory to obtain the dissociation constants of weak organic acids such as substituted benzoic and cinnamic acids in solution. Partition coefficient, supramolecular structure formation and stoichiometry, critical micelle concentration, and binding or association constant of a molecule with another molecule have all been measured by the HRS technique by us. We find that both the symmetry of the molecule and its concentration in the medium play an important role in finding new chemical applications of the technique.     

Size dependence of second-order optical nonlinearity of CdS nanoparticles studied by hyper-Rayleigh scattering

Rutile TiO(2) particles were partly dissolved into aqueous solutions of H(2)SO(4), and the Ti(4+) ions were reprecipitated by adding NH(3) aq. Rutile-anatase coupled TiO(2) particles were prepared by heating the solid recovered after centrifugation of the suspension. The content of anatase (c(A), wt%) could be controlled arbitrarily by changing the dissolved amount of rutile. The photocatalytic activity for the gas-phase oxidation of acetaldehyde was evaluated. The first-order rate constant, k, strongly depended on both c(A) and heating temperature (T(c)), increasing with an increase in T(c) at T(c)相似文献   

Characteristics of charge transfer complexes formed by ferrocene and carbon tetrabromide in solution

Conclusions Ferrocene in solution does not enter into a donor-acceptor interaction with more than one CBr₄ molecule.Translated from Izvestiya Akademii Nauk SSSR, Seriya Khimicheskaya, No. 6, pp. 1399–1401, June, 1988.     

Resonance charge transfer in atom-surface scattering

We present a review of theoretical work on resonance charge transfer in atom-surface scattering. We consider resonance coupling of the atomic level to a wide conduction band, and to low-lying core states. In each case the models, and the methods available for the calculation of the probability of electron transfer are summarised and their applicability demonstrated by selected applications to scattering and sputtering experiments.     

Recent developments in polymeric charge transfer complexes

The recent literature on polymeric charge transfer complexes is reviewed with emphasis on the author's own work. After a definition of the area and a survey of investigations on the spatial arrangement of donor and acceptor sites in the solid state, a variety of applications of these complexes is presented. Electrically conductive polymers are excluded. These applications are: compatibilization of polymer blends, liquid crystalline supramolecular organization, new developments in photo-conductivity, electroluminescence, nonlinear optical properties, photorefractivity and reversible optical storage.     

Gold-nanorod-based sensing of sequence specific HIV-1 virus DNA by using hyper-Rayleigh scattering spectroscopy

Infectious diseases caused by the human immunodeficiency virus (HIV) remain the leading killers of human beings worldwide, and function to destabilize societies in Africa, Asia, and the Middle East. Driven by the need to detect the presence of HIV viral sequence, here we demonstrate that the second-order nonlinear optical (NLO) properties of gold nanorods can be used for screening HIV-1 viral DNA sequence without any modification, with good sensitivity (100 pico-molar) and selectivity (single base-pair mismatch). The hyper-Rayleigh scattering (HRS) intensity increases 45 times when a label-free 145-mer, ss-gag gene DNA, was hybridized with 100 pM target DNA. The mechanism of HRS intensity change has been discussed with experimental evidence for higher multipolar contribution to the NLO response of gold nanorods.     

Electrical properties of polyvinylcarbazole-tetracyanoquinodimethane charge transfer complexes

Electrical properties of polyvinylcarbazole-tetracyanoquinodimethane (PVK:TCNQ) charge transfer complexes were investigated as a function of the composition of the mixture, temperature, pressure and the method of sample preparation. It was shown that the electrical conductivity of the PVK:TCNQ complex (for TCNQ content <10% by weight) increased only slowly with increasing concentration of TCNQ and was only slightly higher than the conductivity of pure PVK. At higher TCNQ concentrations however an abrupt increase of the complex conductivity was observed. This effect may be attributed to the formation of semi-conductive tracks composed of uncomplexed neutral TCNQ molecules. The electrical conductivity of PVK:TCNQ complex was lower than the conductivity of TCNQ alone. The activation energy for electrical conductivity in the complex decreased with increasing TCNQ concentration from 0.99 eV for pure PVK to 0.37 eV for PVK:TCNQ (6:1) complex. The high field conductivity of the PVK:TCNQ complex could be explained by using the Poole-Frenkel model.     

Vibronic coupling in charge transfer complexes. II

Vibronic coupling in excited charge transfer states of crystalline donor—acceptor complexes is reconsidered in relationship to recent electromodulation experiments for anthracene—PMDA. It is demonstrated that vibronic coupling, both linear and quadratic, may substantially affect the electric field dependence of the eigenstates, which may explain, at least semiquantitatively, the observed behaviour. Some consequences for experimental determination of dipole moments by means of electromodulation spectroscopy are pointed out.     

Photodecomposition and charge transfer complexes of acetylferrocene in binary solvents

Photoreactions of acetylferrocene in equimolar binary solvents: CCl₄ — cyclohexane and C₂Cl₄ — cyclohexane were investigated. Photoproducts were identified and the relations between the quantity of photoproducts, their quantum yield, the amount of decomposed acetylferrocene and exposure time and wavelength were determined. Equilibrium constantsK and molar extinction coefficients _c of the CT complexes formed between acetylferrocene and halogen derivative were determined.

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Photochemische Zersetzung und Charge-Transfer-Komplexe von Acetylferrocen in binären Lösungsmitteln

Zusammenfassung Die Photoreaktionen von Acetylferrocen in binären (äquimolaren) Lösungsmittelgemischen — CCl₄/Cyclohexan und C₂Cl₄/Cyclohexan — wurden untersucht. Die Photoprodukte wurden identifiziert und die Abhängigkeit ihrer Menge, der Quantenausbeute und der Menge des zersetzten Acetylferrocens von der Belichtungszeit und der Wellenlänge bestimmt. Die Gleichgewichtskonstanten und die molaren Extinktionskoeffizienten der Charge-Transfer-Komplexe zwischen Acetylferrocen und den Halogenverbindungen wurden ermittelt.

     

Adsorption effects on resonant charge transfer in atom-surface scattering

The probability of positive ionization of an atom impinging on a solid surface is calculated by numerical solution of the equations of motion of the time-dependent molecular orbitals of the system. The model is applied to the scattering of Na atoms, in the energy range 50–1000 eV, from a W(110) surface. The presence of Na adatoms is considered and found to hinder the ionization process. This reduction in the charge-transfer probability arises because of the lowering of the surface work function brought about by increasing adatom concentration.     

Energy transfer in solution of lanthanide complexes

The lanthanides with their well-defined energy levels provide an excellent basis to study different Ln(III)-specific energy transfer processes in a variety of chemical environments. The studies concerning intramolecular and intermolecular energy transfer processes with participation of Ln(III) ions and a variety of ligand groups in solution are reviewed. Phenomena of energy transfer from ligands to Ln(III) ions, resulting consequently in a great enhancement of the Ln(III) ion luminescence (ligand sensitized luminescence), as well as from Ln(III) to other species and between Ln(III) ions are presented.