Determination of the rate constant of oxygen quenching of the excited states of molecules from the singlet oxygen luminescence

We have pioneered a method of determining the rate constant of quenching of the excited electronic states of molecules by molecular oxygen from measurements of the kinetics of photosensitized luminescence of singlet molecular oxygen (^lδ_g). The method can be used in the case where the lifetime of the excited electronic state in an air-saturated solution is comparable with or larger than the luminescence time of the singlet molecular oxygen in the given solvent. It is shown that this situation is implemented on quenching, by molecular oxygen, of the excited triplet states associated with the biopolymers of tetrapyrrole molecules in aqueous (H₂O and D₂O) solutions. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 67, No. 3, pp. 401–404, May–June, 2000.     

Gas-phase photoreactions of anthracene, 2-aminoanthracene,and pyrene with oxygen and water vapors

Excited singlet (S ₁) and triplet (T ₁) state quenching by O₂ and by (O₂ + H₂O) gas-vapor mixtures was studied in the gas phase for polycyclic aromatic hydrocarbons (PAHs, anthracene, 2-aminoanthracene, pyrene). Addition of water vapor is shown not to influence quenching of both fluorescence and delayed fluorescence of PAHs by oxygen. The role of complexes stabilized by charge transfer and hydrogen bonds in quenching the excited states of PAHs by atmospheric gases was analyzed. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 76, No. 3, pp. 342–348, May–June, 2009.     

Photophysical properties of mesonitrophenyl-substituted porphyrins and their dimers at 295 K

It is shown that at 295 K in meso-orthonitrophenyl-substituted octaethylporphyrins and their chemical dimers the steric interactions of the nitro-group and the volume substituents at β-positions of the pyrrole rings favor direct overlapping of molecular orbitals in a donor-acceptor pair. The efficient quenching of fluorescence of the nitroporphyrins in toluene is attributed to direct nonadiabatic electron transfer from the S₁-level of a porphyrin to the lower-lying state with charge transfer by the “through-space” mechanism. Quenching of the T₁-states is related with heat-stimulated transmission to the higher-lying states with charge transfer of the ion-radical pair as well as with enhancement of the probability of the nonradiative T₁→S₀-transition. To whom correspondence should be addressed. Reported at the VIIIth International Conference on Spectroscopy of Porphyrins and Their Analogs, Minsk, September 22–26, 1998. Institute of Molecular and Atomic Physics, National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 4, pp. 531–535, July–August, 1999.     

Delayed luminescence of indole derivatives in the gas phase

Spectral and kinetic characteristics of delayed luminescence of indole derivatives in the gas phase have been studied. The mechanism for delayed luminescence has been shown to depend on the disposition of the two lowest excited singlet ππ*-states, ¹L_a and ¹L_b. For vapors of 3-methyl-and 2,3-dimethylindole having a small ¹L_a-²L_b energy gap ΔE (ΔE < 500 cm⁻¹), prolonged light emissions with maxima at 525 and 540 nm, respectively, have been observed and interpreted as luminescence of free radicals formed due to dissociation of an N-H bond. For vapors of 5-methoxyindole having ΔE ≈ 3700 cm⁻¹, annihilation of delayed luminescence has been observed. The lifetimes for triplet states of 3-methyl-, 2,3-dimethyl-, and 5-methoxyindole at T = 373 K equal to 30, 26, and 65 μsec, respectively, were calculated from the kinetics of the delayed luminescence. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 4, pp. 503–508, July–August, 2008.     

Mechanism for quenching of the luminescence of 9,10-anthraquinone vapor by oxygen

The fluorescence of 9,10-anthraquinone, 1-aminoanthraquinone, 1,4-diaminoanthraquinone, and 1,5-diaminoanthraquinone is not quenched by oxygen because the singlet-triplet energy difference in these compounds is less than the energy needed for excitation of the triplet state of oxygen to the singlet state. Luminescence of 9,10-anthraquinone is quenched because it is mainly phosphorescence, for which the singlet-triplet difference is sufficient for quenching by a mechanism involving singlet oxygen formation. The weak fluorescence of 9,10-anthraquinone is not quenched. The resistance of the fluorescence of 9,10-anthraquinone vapor to quenching by oxygen and the quenching of its phosphorescence explain the different effects of oxygen on the luminescence of α-substituted and β-substituted anthraquinones known from the literature, and indicate that their singlet excited state cannot convert triplet oxygen to singlet oxygen. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 79–4, January–February, 2008.     

Bimolecular gas-phase processes with the participation of vibrationally excited triplet molecules of aromatic ketones

Time-resolved moderated luminescence of aromatic ketones (benzophenone, aceptophenone) in the presence of neutral and reactive hydrogeneous foreign gases (ethylene, pentane, triethylamine) is investigated. It is shown that the addition of hydrogeneous foreign gases leads to strong quenching of the triplet molecules of aromatic ketones. Effectivenesses of such bimolecular processes as the collision detachment of a hydrogen atom and establishment of vibrational and thermal equilibrium are compared. It is concluded that the vibrational degrees of freedom of the acceptors, the aromatic ketones, are inactive in the photochemical process of collision detachment of a hydrogen atom that takes place after the establishment of vibrational equilibrium. Institute of Molecular and Atomic Physics of the National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 1, pp. 73–77, January–February, 1999.     

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.     

Intermolecular Processes in Excited Electronic States in the Gas Phase (Review)

A brief review of works on the temperature dependences of the rate constants k_q of the intermolecular processes proceeding in the excited electronic states in the gas phase is given. The dependences k_q(T) for such biomolecular processes as intermolecular vibrational energy transfer in the triplet state vibrational quasi-continuum, triplet-triplet electron excitation energy transfer, and intermolecular photoinduced electron transfer have been compared. The experimental data have shown that in the gas phase for all analyzed intermolecular processes both an increase and a decrease in k_q with increasing temperature (T) is observed, which is not associated with the specific intermolecular interactions leading to the formation of long-lived components. The change in the type of temperature dependence is due to the change in the mechanisms of the radiationless transitions with increasing density of vibrational levels in the final electronic state. The applicability of the known models based on the theory of radiationless transitions for predicting the temperature dependences k_q(T) is discussed. __________ Translated from Zhurnal Prikladnoi Spektros-kopii, Vol. 72, No. 4, pp. 429–439, July–August, 2005.     

Anomalies in oxygen-induced quenching of electronically excited states of 4,4′-bis[2-(1,3)-benzoxazol-2-yl)ethenyl]biphenyl in the vapor phase

From oxygen-induced quenching of polarized fluorescence of 4,4′-bis[2-(1,3-benzoxazol-2-yl)ethenyl]biphenyl, we have observed structural transformation in electronically excited molecules with retention of fluorescent capability, initiated by collisions with oxygen. Replacing two hydrogen atoms with fluorine in the ortho positions of the diphenyl moiety of the molecule leads to absence of quenching upon collisions with oxygen molecules, owing to the electronegative properties of fluorine atoms. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 6, pp. 902–905, November–December, 2008.     

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.     

Solvatochromic shift of the 0-0 phosphorescence band and change of polarizability in the a 1δg → X 3Σ g? -transition in the oxygen molecule

We used known experimental data to analyze the influence of intermolecular interactions on the position of the 0-0-band a¹Δ_g → X³Σ _g ⁻ phosphorescence of molecular oxygen in solutions. A bathochromic (red) shift caused by dispersion interactions and fluctuations of the internal electric field (induction effect) is analyzed employing new formulas obtained by us in the framework of the Onsager model. The contributions from intermolecular repulsion and higher multipole interactions to the shift of the spectrum are also discussed. It is found that the polarizability in the a¹Δ_g state is higher than in the X³Σ _g ^t- state by 0.19 ± 0.03 ų. Taking into account the induced nature of O₂ phosphorescence in solutions, it is noted that the change of polarizability Δα_eg = 0.19 ų should differ from the change of Δα_eg inherent in free molecular oxygen. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 4, pp. 453–459, July–August, 2007.     

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.     

On the origin of surface states in a correlated local-moment film

The electronic quasiparticle structure of a ferromagnetic local moment film is investigated within the framework of the s-f model. For the special case of a single electron in an otherwise empty energy band being exchange coupled to a fully ordered localised spin system the problem can be solved exactly and, for the spin- electron, some marked correlation effects can be found. We extend our model to incorporate the influence of the surface on the electronic structure. Therefore we modify the hopping integrals in the vicinity of the surface. This leads to the existence of surface states, both for the spin- and the spin- spectral density of states. The interplay between the modification of the hopping integrals and the existence of surface states and correlation effects is discussed in detail. Received: 22 September 1997 / Revised: 12 December 1997 / Accepted: 15 December 1997     

Non-Fermi liquid behavior in the stripe phase of the extended Hubbard model

Within a strong-coupling perturbative approach, based on a Cumulant Expansion of the extended single-band Hubbard model, we show that the on-shell inverse scattering time deviates from the normal Fermi-liquid behavior near the points of the Fermi surface connected by the characteristic wave-vector of an incommensurate charge density wave. The violation of the Fermi liquid behavior is associated with a square root behavior of the inverse quasiparticle lifetime in proximity of a stripe phase. Some relevant features observed in ARPES experiments on Bi2212 are qualitatively reproduced. Received 28 February 2002 / Received in final form 7 May 2002 Published online 9 July 2002     

Effect of the initial phase of the field in ionization by ultrashort laser pulses

We report on observable new features related to ionization of atoms by laser pulses of only few cycles and some intensity. We show that for particular photo-electron energies, the angular distribution becomes asymmetric and that this asymmetry is related to the initial phase of the field. Received: 4 November 1997/Revised: 21 January 1998/Accepted: 23 February 1998     

Theoretical study of neighboring carbonyl group participation in the elimination kinetics of chloroketones in the gas phase

The gas‐phase elimination of kinetics 4‐chlorobutan‐2‐one, 5‐chloropentan‐2‐one, and 4‐chloro‐1‐phenylbutan‐1‐one has been studied using electronic structure methods: B3LYP/6‐31G(d,p), B3LYP/6‐31++G(d,p), MPW91PW91/6‐31G(d,p), MPW91PW91/6‐31++G(d,p), PBEPBE/6‐31G(d,p), PBEPBE /6‐31++G(d,p), and MP2/6‐31++G(d,p). The above‐mentioned substrates produce hydrogen chloride and the corresponding unsaturated ketone. Calculation results of 4‐chlorobutan‐2‐one suggest a non‐synchronous four‐membered cyclic transition state (TS) type of mechanism. However, in the case of 5‐chloropentan‐2‐one and 4‐chloro‐1‐phenylbutan‐1‐one, the carbonyl group assists anchimerically through a polar five‐membered cyclic TS mechanism. The polarization of the C? Cl bond, in the sense of C^δ+…Cl^δ?, is a rate‐determining step in these elimination reactions. The significant increase in rates in the elimination of 5‐chloropentan‐2‐one and 4‐chloro‐1‐phenylbutan‐1‐one is attributed to neighboring group participation due to the oxygen of the carbonyl group assisting the C? Cl bond polarization in the TS. Copyright © 2010 John Wiley & Sons, Ltd.     

Computational (MP2 and DFT) modeling of the substrate/inhibitor interaction with the LDH active pocket in the gas phase and aqueous solution: bimolecular charged (pyruvate/oxamate–guanidinium cation) and neutral adducts (pyruvic/oxamic acids–guanidine)

Two types of bimolecular adducts were studied for the substrate and inhibitor of lactate dehydrogenase (LDH), one type of adducts between ionic species, α‐keto‐carboxylates (pyruvate and oxamate) and the guanidinium cation, and the other type of adducts between neutral species, α‐ketocarboxylic (pyruvic and oxamic) acids and guanidine. Calculations were performed in the gas phase and aqueous solution using the MP2 and PCM methods and the 6‐31++G** basis set. Application of the DFT(B3LYP) and PCM methods led to similar results. A change of the adducts' preference was observed when proceeding from the gas phase to aqueous solution. This change is in good agreement with the acidity–basicity scales in both phases. Formation constant (K_HB) for adduct between neutral species is greater for pyruvic than for oxamic acid in the gas phase, whereas a reverse situation takes place in aqueous solution, where the K_HB value for adduct between ionic species is smaller for pyruvate than for oxamate. The water molecules favor interactions of more polar oxamate with the guanidinium cation. Stronger interaction with this cation, a model of the arginine fragment of the LDH pocket, suggests that oxamate (inhibitor of LDH) has stronger binding properties in aqueous solution than pyruvate (substrate of LDH). Copyright © 2008 John Wiley & Sons, Ltd.     

Femtosecond to nanosecond relaxation time scales in electronically excited tetrakis(dimethylamino)ethylene: identification of the intermediates

In the TDMAE molecule (title molecule), the time evolution has been analyzed from the very initial excitation step down to a fluorescent state, over widely different time scales. Pump probe measurements have been performed at 3 different excitation wavelengths 400, 266 and 200 nm. The decay has been followed over the femtosecond and subnanosecond ranges with this method and the decay of the final charge transfer state has been detected by its fluorescence emission. This allows an overview of the complete decay mechanism. The initial relaxation pathway is interpreted in a similar way to ethylenic molecules, where the initial wavepacket is quickly trapped in a doubly excited state Z with charge transfer character. Then the Z state decays slowly (10-100 picoseconds) into the final state. In difference to monoalkenes the final stage of this evolution is a charge transfer state. The decay of transient Z state to the charge transfer state is a further assessment of the partial ionic character of the Z state. This type of molecule with low ionization potential can be viewed as a demonstrative example of the interrelation between the charge induced forces and the deformations in excited state reaction dynamics. Received 17 January 2001 and Received in final form 23 February 2001     

On the absence of intermediate phases in the two-dimensional Coulomb gas

For a simple, continuum two-dimensional Coulomb gas (with soft cutoff), Gallavotti and Nicoló [J. Stat. Phys. 38:133–156 (1985)] have proved the existence of finite coefficients in the Mayer activity expansion up to order 2n below a series of temperature thresholdsT _n =T [1+(2n–1)^–1] (n=1, 2,...). With this in mind they conjectured that an infinite sequence of intermediate, multipole phases appears between the exponentially screened plasma phase aboveT ₁ and the full, unscreened Kosterilitz-Thouless phase belowT T _KT. We demonstrate that Debye-Hückel-Bjerrum theory, as recently investigated ford=2 dimensions, provides a natural and quite probably correct explanation of the pattern of finite Mayer coefficients while indicating the totalabsence of any intermediate phases at nonzero density ; only the KT phase extends to >0.