Temperature Dependence of the Efficiency of Collisional Transfer of Vibrational Energy in Mixtures of Vibrationally Excited Triplet Molecules with Foreign Gases

By the pressure dependences of the decay rates of delayed fluorescence activated by vibrational excitation of triplet molecules of benzophenone and anthraquinone, the efficiencies of collisional transfer of vibrational energy (V–V-transfer) in the vibrational quasi-continuum of the triplet state have been estimated. It is shown that the efficiencies of the process in mixtures with foreign gases increase with increasing dipole moment and polarizability of colliding molecules. In the temperature range 433–513 K, we obtained an inverse temperature dependence of the V–V-transfer efficiency, which is satisfactorily described by empirical relations taking into account long-range attractive forces. The results obtained point to the determining role of long-range attractive forces in quasi-resonance V–V-transfer of vibrational energy by molecules excited in vibrational quasi-continuum.     

Homo- and Heteroannihilation of Triplet-Excited Bengali Rose and Anthracene Molecules on Silica in a Wide Temperature Range

The processes of triplet-triplet annihilation of the triplet-energy donor of Bengali rose dye and anthracene acceptor adsorbed on the surface of wide-pore silica have been investigated in the temperature range 150–290 K. The rate constants of homo- and heteroannihilation of the molecules of luminophors have been determined in a wide temperature range. It has been established that the processes of energy transfer in the initial (after photoexcitation) periods of phosphorescence decay are described by the Inokuti–Hirayama equations modified in the present work for a two-dimensional problem, whereas in the mean-time and long-time periods the kinetics of phosphorescence decay becomes similar to the fractal one.     

Coverage dependent organic–metal interaction studied by high-resolution core level spectroscopy: SnPc (sub)monolayers on Ag(1 1 1)

We study the electronic structure of tin-phthalocyanine (SnPc) molecules adsorbed on a Ag(1 1 1) surface by high-resolution photoelectron spectroscopy. We particularly address the effect of different SnPc coverages on the interaction and charge transfer at the interface. The results give evidence for a covalent molecule–substrate interaction, which is temperature and coverage dependent. The valence and core level spectra as well as the work function measurements allow us monitoring subtle differences in the strength of the interface interaction, thus demonstrating the sensitivity of the methods. The results consistently show the effect of charge exchange between substrate and molecules which obviously leads to a net charge transfer into the SnPc molecules, and which is increased with decreasing coverage. Surprisingly, the Sn3d core levels are neither effected by variations of charge transfer and interaction strength, nor by a possible “Sn-up” or “Sn-down” orientation, which have been observed for sub-monolayers.     

Theoretical model of triplet-triplet annihilation

The electronic mechanism of triplet-triplet annihilation resulting in the delayed fluorescence of organic molecules in liquid solutions is investigated. There is a discussion of the nature and strength of the interactions which lead to radiationless energy transfer between two triplet-excited molecules in a collision complex, when the first excited singlet state of one of the molecules is filled. The role of intermediate states with charge transfer and also of the unstable excimer state in the contact complex is noted.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 9, pp. 12–17, September, 1978.     

Abnormal adsorption behavior of dimethyl disulfide on gold surfaces

Adsorption of dimethyl disulfide (DMDS) on gold colloidal nanoparticle surfaces has been examined to check its binding mechanism. Differently from previous results, DMDS molecules adsorbed on the gold surface at high concentration showed the S–S stretching band at 500 cm⁻¹ in surface-enhanced Raman scattering (SERS) spectra, which indicates the presence of intact adsorption of DMDS molecules. However, it was found that the S–S bond of disulfides was easily cleaved on the gold surface at low concentration. These behaviors were not observed for diethyl disulfide (DEDS) or diphenyl disulfide (DPDS). Our results indicate that DMDS molecules with the shortest alkyl chains on the gold surface can be inserted into self-assembled monolayers (SAMs) without the S–S bond cleavage during self-assembly due to insufficient lateral van der Waals interaction and the low adsorption activity of disulfides, whereas DEDS with longer alkyl chains or DPDS with the weak disulfide bond dissociation energy would not. These unusual DMDS adsorption behaviors were examined by scanning tunneling microscopy (STM) and X-ray photoelectron spectroscopy (XPS). We also compared the bonding dissociation energy of the S–S bonds of various disulfides by means of a density functional theory (DFT) calculation.     

Modification of polycarbonate surface properties by nano-, micro-, and hierarchical micro–nanostructuring

Polycarbonate surfaces were patterned with nanopillars, microbumps, or nanopillars superimposed on microbumps. Patterning was achieved by applying nanoporous anodized aluminum oxide (AAO) membranes, microstructured aluminum foil, or anodic alumina on microstructured aluminum as mold inserts in injection molding. The effect of the different-sized structures on properties of the polycarbonate surface was investigated in contact angle measurements with water and oleic acid. The water contact angle increased from 82° on the smooth surface to 139° on the hierarchical micro–nanostructure. The transmittance of the polycarbonate increased with nanopatterning, while the reflection properties of the polycarbonate surface decreased. Reflection was lowest for the nanostructure with 53 nm pillar diameter and 77 nm interpillar distance. Values ranged from 0.6 to 1.1% over the whole wavelength range of visible light, which was 4–5% units lower than the corresponding values for the smooth polycarbonate.     

Heterogeneous triplet-triplet annihilation of erythrosine and anthracene molecules on a fractal anodized aluminum surface

We have studied exchange resonance processes of homogeneous triplet-triplet annihilation and heterogeneous triplet-triplet annihilation for erythrosine and anthracene molecules on an anodized aluminum surface over a broad temperature range. We have shown that the kinetics of the considered processes are determined by the dimensionality of the molecular clusters on the porous anodized aluminum surface. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 2, pp. 205–210, March–April, 2007.     

First principle study of a bimolecular thin film on Ag(1 1 1) surface

The formation of melamine–PTCDI bimolecular networks deposited on Ag(1 1 1) is studied by means of first principle calculations. Emphasis is placed on the interplay of the inter-molecular hydrogen bonds and the molecule–substrate contacts. Our simulations show rather strong distortions of the adsorbed molecules near the contact points due to the influence the hydrogen bonds. Despite this, the charge transfer from the substrate to a PTCDI molecule remains almost the same (0.9 e⁻) as obtained for an isolated PTCDI molecule. A detailed analysis of the topological features of the electronic density reveals that the charge transfer modifies the two types of hydrogen bonds in opposite ways, weakening the central bond and strengthening the two lateral ones, while roughly keeping a constant binding energy. Altogether, the influence of the substrate on the molecular network is proved to be weak.     

Influence of the Microstructure of Polymer Gels on the Electron-Excitation Energy Transfer Between Organic Molecules

The electron-excitation energy transfer (EEET) between ionic dyes in polyelectrolyte-network polymers with a different space distribution of charged segments has been investigated. It has been established that the structure of network polymers influences the efficiency of the EEET in them mainly due to the formation of a fractal distribution of interacting molecules. It is shown that the efficiency of the EEET can be controlled by changing the number and arrangement of charged segments of polyelectrolyte networks.__________Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 2, pp. 181–185, March–April, 2005.     

Electrical conduction measurement of thiol modified DNA molecules

We present a novel transport measurement of 60 base pairs of poly(dG)–poly(dC) DNA molecules. Thiol-terminated DNA molecules are chemically anchored at the surface of a Au nanoparticle and this DNA attached Au nanoparticle is self-trapped in between Au nanoelectrodes to make an electrical conduction channel. It provides an automatic electrical conduction channel consisting of electrode–DNA–nanoparticle–DNA–electrode. Due to robust bonding of thiol and Au, this transport channel is stable and reliable. The current–voltage characteristics measured from our device show a nonlinear behavior with voltage gaps comparable to previous experiment using the same molecules.     

Energy transfer between adsorbates by means of surface plasmons

Nonradiative electron excitation energy transfer between the molecules adsorbed by the plane conducting surface is investigated. It is demonstrated that the mechanism with participation of surface plasmons can be efficient for energy transfer in such system. A dependence of the energy transfer rate in the donor-acceptor adsorbate pair on the distance and anisotropy parameters is established. The efficiencies of the direct dipoledipole and plasmon channels of energy transfer are compared. The dominating (exceeding by 1–2 orders of magnitude the energy transfer rate in a system without conducting bodies) contribution of the plasmon mechanism to the total energy transfer rate is detected when molecules are close to the metal surface.     

Quenching of perylene fluorescence by Co2+ ions in dipalmitoylphosphatidylcholine (DPPC) vesicles

We report the fluorescence quenching of perylene by CoCl₂·6H₂O in small unilamellar DPPC vesicles via energy transfer. At the probe-to-lipid ratio of 1200 and quencher to lipid ratios of 12.51, donor-donor energy transfer between clustered perylene molecules was observed as well as energy transfer from the perylene molecules to cobalt ions bothabove andbelow the main phase transition temperature of the lipid. The fluorescence quenching of perylene by CoCl₂·6H₂O in the lipid gel state is shown to be well described by Förster long-range energy transfer when both donor-donor and donor-acceptor energy transfer are considered. In the liquid crystalline phase diffusion of the molecules is described as well as energy transfer. The interaction radiusR ₀ for energy transfer from perylene to Co²⁺ is found to be 13.4±1.1 Å in the gel phase at 303 K, in good agreement with the theoretical value forR ₀ of 13.9 Å. In the liquid crystalline phase at 323 K the lower value obtained forR ₀, 11.3±1.6 Å, is attributed to saturation of the Co²⁺ ions at the interfacial region of the bilayer. A diffusion coefficient of (1.06±0.15)×10^–6 cm² s^–1 is obtained for perylene-cobalt diffusion in the liquid crystalline phase at 323K.     

Impulsive-discharge formation in water

This paper reports on research on an impulsive electrical discharge in deionized water (=2 × 10⁴ · m) in the voltage range 17–50 kV. The research showed that the discharge proceeds through the development of subsonic (U=17–22 kV) or supersonic (U=25–50 kV) streamers, depending on the electric-field strength at the surface of the tip. When voltage impulses having an amplitude of 20–25 kV are unleashed, the development of both types of streamers is observed in the discharge gap. The experiments carried out by the authors do not confirm the hydrodynamic origin of the disturbances at the initiating electrode that give rise to the discharge's development. The authors hypothesize that streamer development is due to the ionization of water molecules. The energy expenditures to ionize the molecules in the streamer channel are estimated.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 1, pp. 88–92, January, 1989.     

Real-time observation on surface diffusion and molecular orientations for phthalocyanine thin films at nanometer spacial resolution

The morphology, electronic structure and ordering of the phthalocyanine thin films have been investigated at nanometer scale by photoelectron emission microscopy (PEEM) excited by polarized soft X-rays from synchrotron light source. The sample investigated was micropattern of silicon phthalocyanine deposited on gold surface. The incident angle dependences of the X-ray absorption near edge structure (XANES) spectra at the silicon K-edge revealed that the molecules of 5-layered films are lying nearly flat on the surface. Clear image of the micropattern was observed by PEEM, showing that the molecules are deposited via Volmer–Weber (VW) mode at room temperature. While, the surface diffusion was observed upon heating, and the micropattern image almost disappeared at 240 °C, representing the deposition mode changes from VW-mode to Frank–van der Merwe (FM)-one. On the basis of the photon-energy dependences of the brightnesses in the PEEM images, it was found that the molecules diffusing to the fresh gold surface rather stand-up at 240 °C. The observed changes in the molecular orientations at nanometer domains are discussed on the basis of the strengths of the molecule–molecule and molecule–surface interactions.     

Photodesorption of H2O molecules from a glass surface and spectral distribution of its efficiency

An experimental arrangement based on an elliptical illuminator has been developed to determine the efficiency of desorption of H₂O molecules from a glass surface. The target is the inner surface of a glass tube welded to a PMI-2 manometric converter. The necessary range of the radiation pulse from an IFP-2000 lamp is separated by a pile of filters from a large collection of colored glass. The energy in a pulse is measured by an evacuated calorimetric detector of cylindrical shape that reproduces the irradiated surface. We have plotted the spectral curve of the efficiency, taking as i₀ the total light flux that penetrates the surface of the glass target. It was found that the red limit of photodesorption of molecules from the surface of glass of the molybdenum group is situated at 470±25 nm, and the absolute maximal value of the efficiency at =330 nm reaches 2·10^–4 mol./photon. The desorption of the molecules is deduced to be essentially photoelectronic in nature.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 3, pp. 3–7, March, 1981.     

Multi-dimensional mixed quantum–classical description of the laser-induced desorption of molecules

A mixed quantum–classical method for the simulation of laser-induced desorption processes at surfaces is implemented. In this method, the nuclear motion is described classically, while the electrons are treated quantum mechanically. The feedback between nuclei and electrons is taken into account self-consistently. The computational efficiency of this method allows a more realistic multi-dimensional treatment of desorption processes. We apply this method to the laser-induced desorption of NO from NiO(100) using a two-state two-dimensional potential energy surface derived from ab initio quantum chemical calculations; we extend this potential energy surface to seven dimensions employing a physically reasonable model potential. By comparing our method to jumping wave-packet calculations on exactly the same potential energy surface we verify the validity of our method. We focus on the velocity, rotational, and vibrational distributions of the desorbing NO molecules. Furthermore, we model the energy transfer to the substrate by a surface oscillator. Including recoil processes in the simulation has a decisive influence on the desorption dynamics, as far as the velocity and rotational distribution is concerned. In particular, the bimodality in the velocity distribution observed in low dimensions and in the experiment disappears in a high-dimensional treatment. PACS  68.43.Tj; 68.43.Rs; 82.20.Gk; 82.20.Wt     

Effect of the Pyranose Ring Conformation on the Vibrational Spectra of Sugar Epoxides

Normal vibrations of two sugar epoxides — methyl 2,3-anhydro-4-deoxy--D-ribohexopyranoside and methyl 3,4-anhydro--D-talohexopyranoside — have been carried out by the molecular mechanics method. Parametrization of the force field used has been performed and the parameters of the oxirane ring for sugar epoxides have been determined. A good agreement between the experimentally observed and calculated frequencies has been obtained. The IR spectral absorption bands of the molecules under investigation in the 1500–400-cm^–1 range have been assigned on the basis of the potential energy distribution function of normal vibrations. The investigation of the potential energy surface of these molecules has shown that their pyranose ring can take conformations close to half-chair, boat, skew boat, and twist forms. Comparative analysis of the normal vibrations of various conformers has revealed that the form of the pyranose ring influences the vibrational spectra of sugar epoxides.     

Boron neutralization and hydrogen diffusion in silicon subjected to low-energy hydrogen implantation

Using the hydrogen neutralization of the boron acceptor, the diffusion of hydrogen is investigated in the temperature range 20 °–160 °C. The hydrogenation is performed by low-energy implantation. We observe a fast initial hydrogen migration, followed by a long-time diffusion phase that is described by an effective diffusion coefficientD _eff=D _{0 eff} exp(–E _a/kT) withD _{0 eff}–cm²s^–1 andE _a=(0.83±0.05) eV. No deeper hydrogen migration is detected for implantation times longer than – 30 min. Our data are explained by the build-up of a large amount of molecular hydrogen beneath the surface, which strongly hinders the transfer of the implanted hydrogen to the bulk. The thermal reactivation kinetics of the neutralized boron show a rapid initial step followed by a longtime thermally activated second order phase, which is limited by the recombination of hydrogen into molecules.     

Nature of the electron-excited states and the mechanism of nonradiative energy transfer in aromatic bifluorophores

Quantum-chemical calculations have been carried out for molecules of the bifluorophores naphthalene-(CH₂)_n-anthracene. The electronic structure and molecular-orbital nature of the excited electronic states of the molecules was analyzed and the rate constants of the photophysical processes were estimated. It is shown that for molecules with n=1, 2, 3 the transfer of excitation energy from the donor fragment (naphthalene) to the acceptor (anthracene) is completely equivalent to internal conversion.The work was done under a grant from the Competition Center of St. Petersburg University.Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Fizika, No. 10, pp. 69–75, October, 1993.     

Porous silicon with β-cyclodextrin modified surface for photoluminescence sensing of organic molecules in gas and liquid phase

Porous silicon surface was modified by photochemically activated hydrosilylation reaction with permethyl-6^I-alkenoylamino-6^I-deoxy-β-cyclodextrins terminated with linear alkenoyl spacers of various lengths. As compared to unmodified surface, derivatized surfaces revealed modified photoluminescence response in the presence of controlled amounts of various organic molecules in gas and liquid phase. For the selected set of analytes we observed most significant modification of photoluminescence response for aromatic compounds what corresponds to optimum molecular size for strong host–guest interaction with β-cyclodextrin cavity. Aliphatic compounds quenched photoluminescence from both unmodified and surface modified porous silicon. For low gas phase concentrations of aromatic analytes β-cyclodextrin modified porous silicon revealed photoluminescence enhancement, at higher concentrations common photoluminescence quenching was observed. The size-dependent host–guest interaction between β-cyclodextrin cavity and detected molecule was observed in photoluminescence quenching in the presence of aliphatic molecules in liquid phase. The role of the strength of host–guest interactions between detected analytes and β-cyclodextrin cavity on photoluminescence sensor response is discussed.