Quenching of liquid scintillator fluorescence by chloroalkanes and chloroalkenes

The fluorescence quenching of 2,5-diphenyloxazole (PPO) by a series of chloroalkanes and chloroalkenes including carbon tetrachloride, chloroform, dichloroethane, tetrachloroethane, dichloroethylene, trichloroethylene and tetrachloroethylene was studied in toluene as solvent at room temperature. CCl₄ was found to be the most efficient quencher in the series. The quenching was found to be appreciable and a positive deviation from linearity was observed in the Stern–Volmer (SV) plots for all the quenchers in the concentration range studied. From the studies of effect of temperature, solvent viscosity and excitation wavelength dependence for the PPO–CCl₄ system, it was inferred that non-linearity is due to the presence of a minor static quenching component in an overall dynamic quenching. The static (K_S) and the dynamic (K_D) quenching constants were calculated from the modified SV equation using quadratic least square fits. Fluorescence quenching experiments with CCl₄ were done for four other scintillators (POPOP, α-NPO, BBO and PBBO). The mechanism of quenching was established to be via charge-transfer, with the direction of transfer being from the scintillators to the chloroalkanes and chloroalkenes.     

Fluorescence Quenching of 2-Amino-9-Hydroxy Fluorene by Chloromethanes

Fluorescence quenching of 2-amino-9-hydroxyfluorene by CCl₄, CHCl₃, and CH₂Cl₂ was investigated in solvents of different polarity. The results reveal that the mechanism of quenching is purely dynamic (complex formed in excited state). The bimolecular quenching-rate constants (k_q) correlate well with electron affinity of the quenchers. They are also dependent on the polarity of the solvents, confirming the formation of charge-transfer nonemissive exciplex.     

Photoinduced Electron Transfer From Carbazole to Halomethanes in a Gas Phase

Intermolecular photoinduced electron transfer (PET) in a gas phase was studied using carbazole vapor fluorescence quenching by halomethanes (CHCl₃, CH₂Br₂, CCl₄, CHBr₃). The fluorescence quenching rate constants k _q changing from 2.3·10⁵ sec^–1·torr^–1 in mixtures with CHCl₃ to 4.6·10⁶ sec^–1·torr^–1 in mixtures with CHBr₃ at a constant temperature of 403 K were estimated. The dependence of the carbazole fluorescence decay rates in the presence of halomethanes on the free energy change G during transfer of the electron from carbazole to halomethanes is considered. It is suggested to take into account the influence of the vibrational energy of the carbazole molecule E _vib and its temperature changes in estimation of the G values. The differences between PET in the gas and liquid phases were analyzed. It is found that for mixtures with CCl₄ and CHBr₃ the negative temperature dependence of k _q is observed, when the decay rates and efficiencies of the intermolecular PET decreased with temperature increase in the range 403–573 K, i.e. these mixtures the electron transfer is not a barrier-restricted process.     

Final-state effects on the assignment of boronK-shell spectra in BF3 molecules

Summary Extensive, bound-state calculations for the electronic ground state of the BF₃ molecule are reported and a simple model is employed to generate its ionic state associated with aK-shell vacancy in the boron atom. The rearrangement of the molecular-charge distribution that follows the initial ionization process is examined within the present model and its effect on the full boron X-ray absorption spectra is discussed. The inadequancy of band classifications which are based only on initialstate calculations in providing anything more than qualitative results is again observed and analysed.

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Riassunto Si riportano estesi calcoliab initio per gli stati elettronici legati della molecola del BF₃ nel suo stato fondamentale e si descrive un modello semplice che permette di ottenere gli stati ionici relativi ad una vacanza nel guscioK dell’atomo di boro. Si esaminano il processo di riarrangiamento della distribuzione di carica molecolare che ha luogo dopo la ionizzazione iniziale ed i suoi effetti sullo spettro di assorbimento X relativo all’atomo centrale. Si evidenzia ed analizza il valore puramente qualitativo di ogni assegnazione delle righe di assorbimento che sia basata unicamente sulla struttura dello stato iniziale non perturbato.

     

The fast and slow rotation approximations for the description of the kinetics of triplet radical quenching and electron spin polarization

The specific features of the mechanisms and kinetics of generation of net chemically induced dynamic electron polarization (CIDEP) in triplet radical quenching (TRQ) in liquids is analysed in detail. The problem reduces to the analysis of fairly strong non-adiabatic transitions between states of the triplet radical spin Hamiltonian which are known to determine CIDEP generation in TRQ. The analysis is performed in two limits of fast and slow rotation of the triplet molecule using the previously developed method of treatment for non-adiabatic transitions. The method made it possible to derive analytical formulas for the CIDEP generation probability P _e and rate K _e, and for the TRQ probability P _q and rate K _q in the case of relatively strong quenching. It is shown that the dependence of K _e on the relative diffusion coefficient D _r is of bell shape and cannot be described correctly by the usually applied relation K _e = K _q P _e.     

Influence of Temperature on Photoinduced Reactions of Organic Molecules in the Gas Phase

The influence of temperature on the rate constants of photoinduced intermolecular electron transfer, representing the first stage of photoinduced reactions, has been investigated based on analysis of the quenching of fluorescence of carbazole vapor by halomethanes (CHCl₃, CH₂Br₂, CCl₄, CHBr₃) and delayed fluorescence of benzophenone and anthraquinone vapors by aliphatic amines (diethylamine, dibutylamine, cyclohexylamine, triethylamine) and pyridine. It has been established that the rate constants of photoinduced electron transfer in different donor-acceptor pairs in the gas phase can increase or decrease with increase in the temperature from 433 to 623 K. The energies of activation and enthalpy of the fluorescence-quenching process have been determined. The interrelation between the rate constants of fluorescence quenching k _q and the free energy of electron transfer G _ET has been analyzed with account for the mean vibrational energy <E _vib> of the interacting molecules. It is shown that positive and negative temperature dependences k _q(T) are characteristic, respectively, of the regions of normal (k _ET increases with decrease in G _ET) and inverted (k _ET decreases with decrease in G _ET) changes in the rate constants caused by an increase in the exothermicity of the photoinduced electron transfer process.     

Some observations related to intermittency and multifractality in Si and C-nucleus collisions at

An attempt is made to study the existence of dynamical fluctuations of relativistic particles using the methods of modified multifractal moments, G_q, and scaled factorial moments, F_q, in terms of new scaled variable X(η) suggested by Bialas and Gazdzicki. For this purpose analyses of experimental and UrQMD data involving interactions of ²⁸Si and ¹²C nuclei at with nuclear emulsion are used. The variation of lnG_q and lnF_q with lnM in pseudorapidity (η) phase space reveals power law behaviour. The values of slopes, τ_q and _q determined from the analyses of G_q and F_q moments are discussed. The generalized fractal dimensions, D_q, determined from the above methods are found to decrease with the order of the moments, q, indicating multifractality in multiparticle production. It is also observed that the spectral function f(α_q) for heavier projectile is much broader than for lighter beam due to larger number of participating nucleons present in heavier projectile.     

NMR,IR, and ESR spectroscopic investigation of reaction of α‐silylamines with carbon tetrachloride

This paper reports about high reactivity of α‐silylamines in the reaction with CCl₄. Unlike Et₃N, α‐silylamines rapidly react with CCl₄ upon irradiation with daylight to form α‐silylamine hydrochloride salts in 92–98% yields. The influence of structure of α‐silylamines and solvent on the degree of conversion was displayed. The interaction of α‐silylamines with CCl₄ was studied by NMR, ESR, and IR spectroscopy. C‐centered radicals of α‐silylamines were detected by ESR spectroscopy with spin traps (MNP, ND, and PBN) in reaction mixtures in CH₃CN and C₆H₆ and it show the radical character of this reaction. Both CH₃CN and C₆H₆ serve as solvents as well as reagents for this reaction. A mechanism of an interaction between α‐silylamines and CCl₄ is discussed. Copyright © 2008 John Wiley & Sons, Ltd.     

Ozone generation in oxygen-fed wire-to-cylinder ozonizer: effect of CH2Cl2, CHCl3 and CCl4 diluents

The inhibition effect of methylene chloride CH₂Cl₂, chloroform CHCl₃ and carbon tetrachloride CCl₄ on the ozone generation process from oxygen by negative corona discharge was experimentally investigated. The experiments were performed in a system of coaxial cylindrical electrodes at total gas pressure of 900 mbar and ambient temperature of gaseous mixtures. The rate of ozone generation as well as ozone concentration apparently decreases with a rising number of substituted chlorine atoms in the methane molecule at constant specific energy consumption dissipated in the discharge and at constant concentration of gaseous impurities in oxygen. In addition to experimental results, the paper presents theoretical considerations aimed at identifying the main process responsible for inhibition of ozone generation. The consumption of considerable fraction of oxygen atoms by CH _x Cl _y–1 radicals formed in discharge, is likely the most important mechanism responsible for the deleterious effect of such compounds on the efficiency of ozone production.     

Co-ordination stoichiometry,edge shift and effective nuclear charge: A novel correlation

Summary K-absorption edge shifts of the absorbing atom in its complexes have been correlated with the effective nuclear charge on the central metal ion, overall electronegativity difference between the nearest neighbours in the complexes and the ionic radius of the central metal ion; a linear correlation has been observed among them, the data subjected to the method of least squares indicated that the correlation is genuine.

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Riassunto Gli slittamenti dell’orlo di assorbimentoK dell’atomo assorbente nei suoi complessi sono stati correlati con la carica nucleare efficacie sullo ione metallico centrale, con la differenza di elettronegatività generale tra vicini prossimi nei complessi e col raggio ionico dello ione metallico centrale; una correlazione lineare è stata osservata tra loro, i dati soggetti al metodo dei minimi quadranti hanno indicato che la correlazione è genuina.

     

Influence of Vibrational Excitation of Triplet Molecules of Anthraquinone on the Photochemical Processes in Gas Mixtures with Amines

By the quenching of the delayed fluorescence (DF) of anthraquinone vapors by aliphatic amines (diethylamine, dibutylamine, cyclohexylamine) and pyridine the photoinduced processes proceeding with the participation of vibrationally excited triplet molecules of anthraquinone have been investigated. The DF quenchingrate constants K _q varying from 1·10⁶ sec^–1·torr^–1 in mixtures with diethylamine to 7·10³ sec^–1·torr^–1 in mixtures with pyridine have been estimated. A correlation between the values of K _q and the ionization potentials of foreign gases confirming the important role of interactions with charge transfer in the quenching of triplet molecules in the gas phase has been established. The influence of other relaxation processes on the DF quenching is considered. It is shown that the intermolecular vibrational relaxation in the T ₁ triplet state leading to the establishment of relaxation equilibrium at a vibrational temperature T _vib considerably increasing the medium temperature is the fastest process among the biomolecular processes (rate constants K _col ^V > 10⁶ sec^–1·torr^–1 > K _q). The values of T _vib and the vibrational energies E _vib of the triplet molecules after the energy exchange in the collisional complex have been estimated. It has been concluded that the photochemical reaction yield is determined by the intermolecular processes proceeding in the T ₁ state at a vibrational equilibrium characterized by high values of T _vib. The influence of E _vib of triplet molecules on the DF quenching rates at a photoinduced electron transfer is considered.     

Photoinduced interaction between MPA capped CdTe QDs and certain anthraquinone dyes

Photoinduced interaction of mercapto propionic acid (MPA) capped CdTe quantum dots (QDs) with certain anthraquinone dyes namely alizarin, alizarin red S, acid blue 129 and uniblue has been studied by steady state and time resolved fluorescence measurements. Addition of anthraquinone dyes to CdTe QDs results in the reduction of electron hole recombination has been observed (i.e., fluorescence quenching). The Stern-Volmer constant (K_SV), quenching rate constant (k_q) and association constants (K) were obtained from fluorescence quenching data. The interaction of anthraquinone dyes with QDs occurs through static quenching was confirmed by unaltered fluorescence lifetime. The occurrence of electron transfer quenching mechanism has been proved by the negative free energy change (ΔG_et) obtained as per the Rehm-Weller equation.     

The effect of high pressure on the electric field gradients at two inequivalent lattice sites of tantalum in ω-zirconium

The pressure variation of the electric field gradients at substitutional tantalum atoms on the two lattice sites (A and B) of ω-zirconium have been determined to be (? lnq ^A/?P)_T = ?1.05(26)10^?3 kbar^?1 and (? lnq ^B/?P)_T = +6.03(40)10^?3 kbar^?1. In addition the thermal expansion coefficients of the unit cell of ω-Zr were found to be α_‖ = +3.5(3)10^?6 K^?6 and α_⊥ = +7.9(4)10^?6 K^?1. A combined analysis of the pressure dependence and the previously determined temperature dependence of the electric field gradients supports the assumption of two different bonding types at the A and B sites.     

Proton coupled electron transfer reaction of phenols with excited state ruthenium(II) – polypyridyl complexes

The reaction of phenols with the excited state, *[Ru(bpy)₃]²⁺ (E₀ = 0.76 V) and *[Ru(H₂dcbpy)₃]²⁺, (dcbpy = 4,4′‐dicarboxy‐2,2′‐bipyridine) (E₀ = 1.55 V vs. SCE) complexes in CH₃CN has been studied by luminescence quenching technique and the quenching is dynamic. The formation of phenoxyl radical as a transient is confirmed by its characteristic absorption at 400 nm. The k_q value is highly sensitive to the change of pH of the medium and ΔG⁰ of the reaction. Based on the treatment of k_q data in terms of energetics of the reaction and pH of the medium, proton coupled electron transfer (PCET) mechanism has been proposed for the reaction. Copyright © 2010 John Wiley & Sons, Ltd.     

Dark material by fast protons on frozen methane

Summary We describe in detail techniques and qualitative results of experiments conduced in our laboratory at Catania (Italy) on the production of stable residing dark (polymerlike) material obtained by bombarding methane frosts with fast (100÷1500) keV proton beams. We give, in particular, results on the cross-section of the process and show that this occurs along the intere ion path so that thick residues are obtained. The thickness of the residues has been measured by bothin situ and remote analysis that also give information on the surface roughness and on the chemical composition. The purpose of the experiments is to get some insight into the possibility that the interaction between energetic ions and hydrocarbon frosts is responsible of the build-up of dark carbonaceous materials widely thought to be present in many astrophysical scenarii. Some astrophysical applications are, in fact, discussed in a correlated paper.

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Riassunto Si descrivono in dettaglio tecniche e risultati quantitativi di esperimenti condotti nel nostro laboratorio di Catania e riguardanti la produzione di materiali scuri (di tipo polimerico) resistenti a temperatura ambiente ed ottenuti dal bombardamento di metano congelato tramite fasci di protoni veloci ((100÷1500) keV). In particolare, si presentano risultati sulla sezione d'urto del processo e si mostra che questo avviene lungo l'interocammino dello ione cosicchè si ottengono residui spessi. Lo spessore di essi è stato misurato siain situ che in un'analisi remota e ciò consente di ottenere informazioni sulla topografia superficiale e sulla composizione chimica. Lo scopo degli esperimenti è di far luce sulla possibilità che l'interazione tra ioni energetici e idrocarburi congelati sia responsabile della formazione di materiale scuro carbonioso che si ritiene ampiamente presente in molti contesti astrofisici. Alcune applicazioni astrofisiche sono infatti discusse in un lavoro connesso al presente.

     

Accurate equilibrium structures of fluoro- and chloroderivatives of methane

This work is a systematic study of molecular structure of fluoro-, chloro-, and fluorochloromethanes. For the first time, the accurate ab initio structure is computed for 10 molecules (CF₄, CClF₃, CCl₂F₂, CCl₃F, CHClF₂, CHCl₂F, CH₂F₂, CH₂ClF, CH₂Cl₂, and CCl₄) at the coupled cluster level of electronic structure theory including single and double excitations augmented by a perturbational estimate of the effects of connected triple excitations [CCSD(T)] with all electrons being correlated and Gaussian basis sets of at least quadruple-ζ quality. Furthermore, when possible, namely for the molecules CH₂F₂, CH₂Cl₂, CH₂ClF, CHClF₂, and CCl₂F₂, accurate semi-experimental equilibrium (r^SE_e) structure has also been determined. This is achieved through a least-squares structural refinement procedure based on the equilibrium rotational constants of all available isotopomers, determined by correcting the experimental ground-state rotational constants with computed ab initio vibration–rotation interaction constants and electronic g-factors. The computed and semi-experimental equilibrium structures are in excellent agreement with each other, but the r^SE_e structure is generally more accurate, in particular for the CF and CCl bond lengths. The carbon–halogen bond length is discussed within the framework of the ligand close-packing model as a function of the atomic charges. For this purpose, the accurate equilibrium structures of some other molecules with alternative ligands, such as CH₃Li, CF₃CCH, and CF₃CN, are also computed.     

Fluorescence quenching of fluorescein by Merocyanine 540 in liposomes

The fluorescence quenching of fluorescein (FL) by merociyanine 540 (MC540) was examined in L-egg lecithin phosphatidycholine (PC) liposomes using spectroscopic methods. The type of quenching mechanism (dynamic or static) was evaluated using the Stern-Volmer plots. Findings were also supported by the temperature studies and florescence decay measurements. The Stern-Volmer equation was utilized to calculate bimolecular quenching constants (K_q). Furthermore, the bimolecular quenching constant of the quencher in the liposomes (K_SV), partition coefficient (K_p), binding constant (K), and corresponding thermodynamic parameters ΔH, ΔS, and ΔG were calculated. The quenching property was also used in determining quantitatively (K_p) the partition coefficient of Merociyanini 540 in PC liposome.The obtained data indicated that static quenching occurred in the system and the K_SV values decreased with increasing lipid concentration. In addition, thermodynamic analysis suggested that van der Waals interactions and hydrogen bonding were the main acting forces between fluorescein and merociyanine 540 molecules in the medium.     

Local electronic structures at selected sites of intermetallic perovskites Mn3MeX (Me=divalent metal,X=N,C)

Summary We have measured the XANES (X-ray absorption near edge structure) spectra on the manganese and metal MeK-edges of the intermetallic perowskites Mn₃MeX (X=N, Me=Mn, Cu, Zn, Ga, Sn; X=C, Me=Ga, Sn) to investigate the distribution on the partial density of the empty states. The information on the local electronic structure at the two differents sites, obtained from the spectra in the first 10 eV above the onset, is discussed in terms of one-electron band model. The relative shape changes in the spectra between the different compounds are explained by the different magnitude of hybridization between the electronic states of different atoms and/or the filling of the empty band by the electrons supplied by the substituted metal. Moreover, information about the local geometrical structure has been obtained from the (10÷50) eV range of the spectra.

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Riassunto La distribuzione della densità parziale degli stati vuoti nelle perovskiti intermetalliche Mn₃MeX (X=N, Me=Mn, Cu, Zn, Ga, Sn; X=C, Me=Ga, Sn) è stata studiata mediante spettroscopia XANES (X-ray absorption near edge structure) alle soglieK del Mn e del metallo Me. Le informazioni sulla struttura elettronica locale di entrambi i siti, ottenute dall’analisi dei primi 10 eV degli spettri XANES, sono discussed in termini di un modello proposto. Il cambiamento relativo della forma negli spetttri dei diversi composti è posto in relazione alla differente ibridizzazione tra stati di atomi diversi e/o dal riempimento degli stati della banda vuota con elettroni forniti dal metallo sostituente. Sono state anche ottenute informazioni sulla struttura geometrica locale analizzando gli spettri nell’intervallo da 10 a 50 eV.

     

Degree Complexity of Birational Maps Related to Matrix Inversion

For a q × q matrix x = (x _{i, j} ) we let ${J(x)=(x_{i,j}^{-1})}For a q × q matrix x = (x _{i, j} ) we let J(x)=(x_i,j^-1){J(x)=(x_{i,j}^{-1})} be the Hadamard inverse, which takes the reciprocal of the elements of x. We let I(x)=(x_i,j)^-1{I(x)=(x_{i,j})^{-1}} denote the matrix inverse, and we define K=I°J{K=I\circ J} to be the birational map obtained from the composition of these two involutions. We consider the iterates Kⁿ=K°?°K{K^n=K\circ\cdots\circ K} and determine the degree complexity of K, which is the exponential rate of degree growth d(K)=lim_n?￥( deg(Kⁿ) )^1/n{\delta(K)=\lim_{n\to\infty}\left( deg(K^n) \right)^{1/n}} of the degrees of the iterates. Earlier studies of this map were restricted to cyclic matrices, in which case K may be represented by a simpler map. Here we show that for general matrices the value of δ(K) is equal to the value conjectured by Anglès d’Auriac, Maillard and Viallet.