Role of charge-transfer complexes in oxygen quenching of excited states of anthracene derivatives in the gas phase

Oxygen quenching of excited triplet and singlet states of gas-phase anthracene and its derivatives that have similar energies of the lower triplet levels but widely different oxidation potentials (0.44 < E_ox < 1.89 V) was studied. Quenching rate constants for singlet (k_S^O2) and triplet (k_T^O2) states in addition to the fraction of oxygen-quenched singlet and triplet states q_{S 1}(T₁^O2 were determined from the decay rates, fluorescence intensities, and delayed fluorescence as functions of oxygen pressure. It was found that k_S^O2 values vary from 2·10⁴ (9,10-dicyanoanthracene) to 1.2·10⁷ sec⁻¹·torr⁻¹ (anthracene, 9-methylanthracene, 2-aminoanthracene) and k_S^O2 values from 5·10² to 1·10⁵ sec⁻¹·torr⁻¹. The k_S^O2 values for anthracene, 9-methylanthracene, and 2-aminoanthracene, which have fast rates of interconversion from S₁ to T₁, are close to the rate constants for gas-kinetic collisions and are independent of the oxidation potentials (E_ox). The quenching rate constants k_S^O2 for the other anthracene derivatives and k_T^O2 for all studied compounds decrease with increasing free energy of electron transfer ΔG_ET, which indicates the important role of charge-transfer interactions in the oxygen quenching of singlet S_1- and triplet T₁ states. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 75, No. 1, pp. 36–42, January–February, 2008.     

Photophysics of bis-bipyridyl complexes of ruthenium(II) with triphenylphosphine

We studied the spectral-luminescent characteristics of the luminescence of mixed-ligand polypyridine-phosphine complexes of ruthenium(II) cis-[Ru(bpy)₂(PPh₃)X](BF₄) _n with ligands 2,2′-bipyridyl (bpy) and triphenylphosphine (PPh₃) and X = Cl⁻, Br⁻, CN⁻, NO₂⁻, NH₃, MeCN, pyridine (py), 4-aminopyridine (pyNH₂), and 4,4′-bipyridyl (4,4′-bpy) in a 4: 1 EtOH-MeOH alcoholic mixture at 77 K. The radiative and nonradiative deactivation rate constants of the lowest electronically excited state of the complexes are determined. We find that triphenylphosphine has a greater effect on the photophysical characteristics of ruthenium(II) complexes compared to π-acceptor strong-field ligands, such as MeCN, CN⁻, and NO₂⁻. At the same time, the characteristics of complexes cis-[Ru(bpy)₂(PPh₃)X] ⁿ⁺ considerably depend on the nature of the second monodentate ligand X, which is coordinated to ruthenium(II), and correlate with its position in the spectrochemical series of ligands.     

Quantum beats in excitons in Cu2O

A theoretical study is carried out of quantum beats (QB) in the time-dependent intensities of absorption of a test pulse and of spontaneous luminescence in a Cu₂O crystal under conditions of double optical resonance. It is assumed that pumping is effected by a CO₂-laser pulse which dynamically couples the exciton levels 1s(Γ ₅ ⁺ ) and 2p(Γ ₄ ⁻ ,Γ ₅ ⁻ ,Γ ₃ ⁻ Γ ₂ ⁻ ) and splits them into two or three pairs of quasi-energy levels. The frequency of the test pulse is in resonance with the frequency Γ ₅ ⁺ of the exciton. The corresponding intensities for various directions of the electric vector of the pump field E _L, the polarization vector ξ, and the wave vector q of the test pulse are obtained. The frequency of the quantum beats is twice the Rabi frequency, which for different values of E _L, ξ and q contains different sets of matrix elements of the dipole transitions between the levels 1s(Γ ₅ ⁺ ) and 2p(Γ ₄ ⁻ ,Γ ₅ ⁻ ,Γ ₃ ⁻ Γ ₂ ⁻ ). Thus, by measuring the period of the quantum beats it is possible to determine the unknown matrix elements of the indicated transitions. Fiz. Tverd. Tela (St. Petersburg) 39, 844–847 (May 1997)     

Improvement of perturbation theory in QCD for e + e − →hadrons and the problem of α s freezing

A method of improving perturbation theory in QCD is developed which can be applied to any polarization operator. The case of the polarization operator Π(q ²), corresponding to the process e ⁺ e ⁻→ hadrons, is considered in detail. By the use of the analytical properties of Π(q ²) and a perturbation expansion of Π(q ²) for q ²<0, the function ImΠ(q ²) at q ²>0 is defined in such a way that the infrared pole is eliminated. The convergence of the perturbation series for R(q ²)=σ(e ⁺ e ⁻ →hadrons)/(e ⁺ e ⁻→μ ⁺ μ ⁻) is improved. After substitution of R(q ²) into the dispersion relation an improved Adler function D(q ²) is obtained, having no infrared pole and a frozen α _s (q ²). Good agreement with experiment is achieved. Pis’ma Zh. éksp. Teor. Fiz. 70, No. 3, 167–170 (10 August 1999) Published in English in the original Russian journal. Edited by Steve Torstveit.     

Electronic and electronic-vibrational phenomena in the new organic conductor ϰ-(ET)2[Hg(SCN)2Cl] with a metal-insulator transition

The reflection spectra and optical conductivity spectra of the new organic conductor ϰ-(ET)₂[Hg(SCN)₂Cl] with a metal-insulator transition in the spectral regions 700–5500 and 9000–40 000 cm⁻¹ have been studied in polarized light at 300 K. A comparisonis made between the spectra obtained and the corresponding spectra of related isostructural conductors based on the ET molecule, and also the properties of the crystal structure of the investigated compounds. An electronic transition between the ET molecules of the dimer (ET) ₂ ⁺ in the spectral region 700–5500 cm⁻¹ has been identified, as have the features of the electronic-vibrational structure arising as a consequence of the interaction of this transition with the completely symmetric intramolecular vibrations of the ET molecule. It is found that the conductor with the stronger dimer interaction between the ET molecules has the higher the transition temperature. Fiz. Tverd. Tela (St. Petersburg) 39, 1313–1319 (August 1997)     

Calculation of the quenching rate constants for electronically excited singlet molecular nitrogen

The quenching rate constants for the singlet states (a′)⁽¹⁾Σ _u ⁻ (v = 1−17), a ⁽¹⁾Π _g (v = 0−14), and w ⁽¹⁾Δ _u (v = 0−13) of molecular nitrogen colliding with an N₂ molecule are calculated using quantum-chemical approximations. It is shown for the first time that both the intramolecular and intermolecular processes of electronic excitation transfer are significant for these states. Calculated rate constants are in satisfactory agreement with experimental data.     

Nonadiabatic effects in the phonon spectra of superconductors

The nonadiabatic corrections to the self-energy part Σ_s(q, ω) of the phonon Green’s function are studied for various values of the phonon vectors q resulting from electron-phonon interactions. It is shown that the long-range electron-electron Coulomb interaction has no direct influence on these effects, aside from a possible renormalization of the corresponding constants. The electronic response functions and Σ_s(q, ω) are calculated for arbitrary vectors qand energy ω in the BCS approximation. The results obtained for q=0 agree with previously obtained results. It is shown that for large wave numbers q, vertex corrections are negligible and Σ_s(q, ω) possesses a logarithmic singularity at ω=2Δ, where Δ is the superconducting gap. It is also shown that in systems with nesting, Σ_s(Q, ω) (where Q is the nesting vector) possesses a square-root singularity at ω=2Δ, i.e., exactly of the same type as at q=0. The results are used to explain the recently published experimental data on phonon anomalies, observed in nickel borocarbides in the superconducting state, at large q. It is shown, specifically, that in these systems nesting must be taken into account in order to account for the emergence of a narrow additional line in the phonon spectral function S(q, ω)≈−π ⁻¹ Im D _s (q, ω), where D _s (q, ω) is the phonon Green’s function, at temperatures T<T _c . Zh. éksp. Teor. Fiz. 115, 1799–1817 (May 1999)     

NMR-ON measurements of187WFe,182,183,186ReNi,186ReFe and203PbFe

The magnetic hyperfine splitting frequencies of¹⁸⁷WFe,¹⁸²Re(j ^π=2⁺)Ni,¹⁸³ReNi,¹⁸⁶ReNi,¹⁸⁶ReFe and²⁰³PbFe in a zero external magnetic field have been determined by the NMR-ON method at about 7 mK as 225.56(6), 130.9(1), 98.17(4), 136.6(4), 1007.0(3) and 58.43(3) MHz, respectively. With the knowng-factors ofg(¹⁸⁶Re, 1⁻)=1.739(3) andg(²⁰³Pb, 5/2⁻)=0.27456(20), the following hyperfine fields were deduced:B _HF(¹⁸⁶ReNi)=−103.05(35) kG;B _HF(¹⁸⁶ReFe)=−759.7(13) kG;B _HF(²⁰³PbFe)=+279.18(25) kG. Taking hyperfine anomalies into account, theg-factor of¹⁸³Re was deduced as |g(¹⁸³Re, 5/2⁺)|=1.267(6). With the assumption of Knight shift factorK=0, theg-factors of¹⁸²Re and¹⁸⁷W and the hyperfine field of¹⁸⁷WFe were determined as |g(¹⁸²Re, 2⁺)|=1.63(5), |g(¹⁸⁷W, 3/2⁻)|=0.414(10) andB _HF(¹⁸⁷WFe) =−714(18) kG. The large hyperfine anomaly was deduced to be¹⁸³W Δ¹⁸⁷W =−0.124(22).     

Studies of parity and time reversal symmetries in neutron scattering from165Ho

We describe searches for parity and time reversal violations in the scattering of polarized neutrons from polarized and aligned¹⁶⁵Ho targets. We have completed a search with 7.1 and 11.0 MeV neutrons for P_oddT_odd terms in the elastic scattering forward amplitude of the form s. (I×K), wheres is the neutron spin,I is the target spin andk is the neutron momentum vector. The target was a single crystal of holmium, polarized horizontally along itsb axis by a 1 Tesla magnetic field. The neutrons were polarized vertically. Differences in the neutron transmission were measured for neutrons with spins parallel (antiparallel) toI×k. The P,T violating analyzing powers were found to be consistent with zero at the few 10⁻³ level: ρ_P,T(7.1 MeV)=−0.88 (±2.02) x 10⁻³, ρ_P,T(11.0 MeV)=−0.4 (±2.88) x 10⁻³. We have also attempted to find enhancements with MeV neutrons in P-violation due to the term s\k. We are preparing an aligned target cryostat for investigations of P_evenT_odd terms {bd(I\k)(I×k)\s} in neutron scattering. The target will be a single crystal cylinder of¹⁶⁵Ho cooled to 100 mK in a bath of liquid helium and rotated by a shaft from a room temperature stepping motor. The cylinder will be oriented vertically and the alignment (c) axis oriented horizontally. Warming or rotation of the sample allows one to separate effects that mimic the sought-after time reversal violating term.     

Progress in pion-decay channelling: Refractory bcc metals at high and low temperatures

By means of π⁺/μ⁺ channelling, positive pions (π⁺) implanted intoTa, Mo, andW are investigated up to high temperatures. A striking observation is that the channelling effect disappears in a rather narrow temperature interval centred at 0.26 (Ta) to 0.51 (W) of the melting temperature. From studies of π⁺ trapping by oxygen atoms inTa estimates for the low-temperature π⁺ diffusivity inTa [D _π(23K)=1.4·10^−10±0.3 m²s⁻¹,D _π(47K)=5.7·10^−10±0.3 m²s⁻¹] as well as for the binding enthalpy of π⁺ to 0 atoms (H _B=7·10⁻² eV) have been obtained. The diffusion data are in reasonable agreement with the theory of phonon-assisted tunnelling.     

Pseudovector heavy quarkonia in e + e −2 collisions

It is shown that BR(χ _b1(1 P)→e ⁺ e ⁻)≃3.3· 10⁻⁷ and BR(χ _c1(1 P)→e ⁺ e ⁻)≃10⁻⁸. This gives realistic possibilities for searching for the production of χ _b1(1 P) and ξ _c1(1 P) states in e ⁺ e ⁻ collisions, even on the present-day colliders, to say nothing of b and c-τ factories. Pis’ma Zh. éksp. Teor. Fiz. 63, No. 8, 569–574 (25 April 1996)     

Rare t-quark decays t → clj+lk? and t → c?jvk induced by doublets of scalar leptoquarks within the minimal four-color-symmetry model

The rare t-quark decays t → cl _j ⁺ l _k ⁻ and t → cṽ _j k _k induced by scalar-leptoquark doublets are considered within the minimal model involving four-color quark-lepton symmetry and the Higgs mechanism of quark and lepton mass splitting. The partial widths with respect to the decays being considered and the total widths Γ(t → cl ⁺′l ⁻) = Σ_j,k Γ(t → cl _j ⁺ l _k ⁻ ) and Γ(t → cl ⁺′l ⁻) = Σ_j,kΓ(t → cṽ _j v _k ) with respect to, respectively, the charged leptonic and neutrino modes are calculated. It is shown that, at scalar-leptoquark masses higher than the t-quark mass (m _S > m _t), the branching ratios for these modes are Br(t → cl ⁺′l ⁻) ≈ (3.5−0.4) × 10⁻⁵ and Br(t → cṽ′v) ≈ (7.1−0.8) × 10⁻⁵ at m _s = 180–250 GeV and an appropriate value of the leptoquark-mixing angle (sin β ≈ 0.2) and can increase for m _S < m _t to Br(t → cl ⁺′l ⁻) ≈ 0.03−0.002 and Br(t → cl ⁺′l ⁻) ≈ 0.46−0.05 for the charged mode at m _S = 150–170 GeV for sin β ≈ 1 and sin β ≈ 0.2, respectively. In the cases being considered, t-quark decays to pairs of charged leptons can be accessible to detection at LHC. In the last case, these decays could manifest themselves (for example, in dilepton events) at the Tevatron as well. Original Russian Text ? P.Yu. Popov, A.D. Smirnov, 2006, published in Yadernaya Fizika, 2006, Vol. 69, No. 6, pp. 1006–1016.     

A diamine ligand with long “arms” and its corresponding dinuclear rhenium(I) complex: Synthesis,characterization, photophysical property,and sensing activity towards molecular oxygen

In this paper, we synthesize a novel diamine ligand of 4,7-dinonadecyl-1,10-phenanthroline (DN-Phen) with two long alkyl chain arms serving as a shield and its corresponding dinuclear Re(I) complex of Re₂(CO)₆(bpy)(DN-Phen)₂ (bpy=4,4′-bipyridine), aiming at an optical sensor immune to the surrounding interferences. Its geometric and electronic structures are investigated, which suggest that the introduced long alkyl chains act as a shield for the excited state of emissive center. The promising photophysical parameters of Re₂(CO)₆(bpy)(DN-Phen)₂, including the immunity of emission towards the surrounding interferences and long excited state lifetime, make itself a potential probe for oxygen detection. By doping Re₂(CO)₆(bpy)(DN-Phen)₂ into two silica matrixes of MCM-41 and SBA-15, oxygen sensing performances of the resulted composite materials are investigated. Finally, a high sensitivity of 20.1 is realized, with short response/recovery time of 8 s/42 s. Here, sensitivity is defined as the ratio of emission maximum under pure nitrogen to emission minimum under pure oxygen, response and recovery times are the times for a sample to lose (response time) or recover (recovery time) 95% of its emission maximum upon periodically changed atmosphere.     

T-band phenomena in 183Re

Abstact: High-spin states in ¹⁸³Re have been studied using the ¹⁷⁶Yb(¹¹B,4n) reaction at 52 and 57 MeV. Two high-K bands have been observed directly by a time-correlated γ-γ coincidence measurement. One of the bands is built on an isomeric K ^π=(25/2)⁺ state at E _x= 1908 keV with a half-life of 0.82(2) ms. The other band, assigned as K ^π=(29/2)⁻ at E _x= 2739 keV, decays to the (25/2)⁺ band. These bands are interpreted as three-quasiparticle structures, π(5/2)⁺[402] &⊗ν(9/2)⁺[624] ⊗ν(11/2)⁺[615] for the (25/2)⁺ band and π(9/2)⁻[514] ⊗ν(9/2)⁺[624] ⊗ν(11/2)⁺[615] for the (29/2)⁻ band. The K ^π= (29/2)⁻ band becomes strongly Coriolis mixed with increasing spin and is gradually changing into a low-K s-band structure. Received: 20 April 1998     

Integrable Nonlinear Evolution Equations on a Finite Interval

Let q(x,t) satisfy an integrable nonlinear evolution PDE on the interval 0<x<L, and let the order of the highest x-derivative be n. For a problem to be at least linearly well-posed one must prescribe N boundary conditions at x=0 and n−N boundary conditions at x=L, where if n is even, N=n/2, and if n is odd, N is either (n−1)/2 or (n+1)/2, depending on the sign of ∂ⁿ_xq. For example, for the sine-Gordon (sG) equation one must prescribe one boundary condition at each end, while for the modified Korteweg-de Vries (mKdV) equations involving q_t+q_xxx and q_t−q_xxx one must prescribe one and two boundary conditions, respectively, at x=0. We will refer to these two mKdV equations as mKdV-I and mKdV-II, respectively. Here we analyze the Dirichlet problem for the sG equation, as well as typical boundary value problems for the mKdV-I and mKdV-II equations. We first show that the unknown boundary values at each end (for example, q_x(0,t) and q_x(L,t) in the case of the Dirichlet problem for the sG equation) can be expressed in terms of the given initial and boundary conditions through a system of four nonlinear ODEs. We then show that q(x,t) can be expressed in terms of the solution of a 2×2 matrix Riemann-Hilbert problem formulated in the complex k-plane. This problem has explicit (x,t) dependence in the form of an exponential; for example, for the case of the sG this exponential is exp {i(k−1/k)x+i(k+1/k)t}. Furthermore, the relevant jump matrices are explicitly given in terms of the spectral functions {a(k),b(k)}, {A(k),B(k)}, and , which in turn are defined in terms of the initial conditions, of the boundary values of q and of its x-derivatives at x=0, and of the boundary values of q and of its x-derivatives at x=L, respectively. This Riemann-Hilbert problem has a global solution.     

Static charged spheres with anisotropic pressure in general relativity

We report a generalization of our earlier formalism [Pramana, 54, 663 (1998)] to obtain exact solutions of Einstein-Maxwell’s equations for static spheres filled with a charged fluid having anisotropic pressure and of null conductivity. Defining new variables: w=(4π/3)(ρ+ε)r ², u=4πξr ², v _r=4πp _r r ², v _⊥=4πp _⊥ r ²[ρ, ξ(=−(1/2)F ₁₄ F ¹⁴), p _r, p _⊥ being respectively the energy densities of matter and electrostatic fields, radial and transverse fluid pressures whereas ε denotes the eigenvalue of the conformal Weyl tensor and interpreted as the energy density of the free gravitational field], we have recast Einstein’s field equations into a form easy to integrate. Since the system is underdetermined we make the following assumptions to solve the field equations (i) u=v _r=(a ²/2κ)r ⁿ⁺², v _⊥=k ₁ v _r, w=k ₂ v _r; a ², n(>0), k ₁, k ₂ being constants with κ=((k ₁+2)/3+k ₂) and (ii) w+u=(b ²/2)r ⁿ⁺², u=v _r, v _⊥−v _r=k, with b and k as constants. In both cases the field equations are integrated completely. The first solution is regular in the metric as well as physical variables for all values of n>0. Even though the second solution contains terms like k/r ² since Q(0)=0 it is argued that the pressure anisotropy, caused by the electric flux near the centre, can be made to vanish reducing it to the generalized Cooperstock-de la Cruz solution given in [14]. The interior solutions are shown to match with the exterior Reissner-Nordstrom solution over a fixed boundary. Dedicated to Prof. F A E Pirani.     

Synthesis,Characterization, DNA Binding Properties,Fluorescence Studies and Toxic Activity of Cobalt(III) and Ruthenium(II) Polypyridyl Complexes

The new ligand 4-(isopropylbenzaldehyde)imidazo[4,5-f ][1,10]phenanthroline (ippip) and its complexes [Ru(phen)₂(ippip)]²⁺(1),[Co(phen)₂(ippip)]³⁺(2),[Ru(bpy)₂(ippip)]²⁺(3),[Co(bpy)₂(ippip)]³⁺(4)(bpy=2,2-bipyridine) and (phen=1,10-phenanthroline) were synthesized and characterized by ES⁺-MS, ¹H and ¹³C NMR. The DNA binding properties of the four complexes were investigated by different spectrophotometric methods and viscosity measurements. The results suggest that complexes bind to calf thymus DNA (CT-DNA) through intercalation. When irradiated at 365 nm, the complexes promote the photocleavage of pBR322 DNA, and complex 1 cleaves DNA more effectively than 2, 3, 4 complexes under comparable experimental conditions. Furthermore, photocleavage studies reveal that singlet oxygen (¹O₂) plays a significant role in the photocleavage.     

Spectral Estimates for Periodic Jacobi Matrices

 We obtain bounds for the spectrum and for the total width of the spectral gaps for Jacobi matrices on ℓ²(ℤ) of the form (Hψ) _n =a _n−1 ψ _n−1 +b _nψ _n +a _nψ _n+1 , where a _n=a _n+q and b _n=b _n+q are periodic sequences of real numbers. The results are based on a study of the quasimomentum k(z) corresponding to H. We consider k(z) as a conformal mapping in the complex plane. We obtain the trace identities which connect integrals of the Lyapunov exponent over the gaps with the normalised traces of powers of H. Received: 17 April 2002 / Accepted: 1 October 2002 Published online: 13 January 2003 Communicated by B. Simon     

Steady State and Time-Resolved Fluorescence Studies of a Hemagglutinin from Moringa oleifera

The saccharide binding and conformational characterization of a hemagglutinin, a low molecular weight protein from the seeds of Moringa oleifera was studied using steady state and time resolved fluorescence. The lectin binds sugars LacNAc (K _a = 1380 M⁻¹) and fructose (K _a = 975 M⁻¹), as determined by the fluorescence spectroscopy. It has a single tryptophan per monomer which is exposed on the surface and is in a strong electropositive environment as revealed by quenching with iodide. Quenching of the fluorescence by acrylamide involved both static (K _s = 0.216 M⁻¹) and collisional (K _sv = 8.19 M⁻¹) components. The native protein showed two different lifetimes, τ ₁ (1.6 ns) and τ ₂ (4.36 ns) which decrease and get converted into a single one, (2.21 ns) after quenching with 0.15 M acrylamide. The bimolecular quenching constant, k _q was 7.55 × 10¹¹ M⁻¹ s⁻¹. ANS binding studies showed that the native protein has exposed hydrophobic patches which get further exposed at extreme acidic or alkaline pH. However, they get buried in the interior of the protein in presence of 1 M GdnHCl or urea.     

New approach in theory of Clebsch-Gordan coefficients foru(n) andU q(u(n))

A new method for calculation of Clebsch-Gordan coefficients (CGCs) of the Lie algebrau(n) and its quantum analogU _q(u(n)) is developed. The method is based on the projection operator method in combination with the Wigner-Racah calculus for the subalgebrau(n−1) (U _q(u(n−1))). The key formulas of the method are couplings of the tensor and projection operators and also a tensor form of the projection operator ofu(n) andU _q(u(n)). It is shown that theU _q(u(n)) CGCs can be presented in terms of theU _q(u)(n−1)) q−9j-symbols. Presented at the 9th International Colloquium: “Quantum Groups and Integrable Systems”, Prague, 22–24 June 2000. Supported by Russian Foundation for Fundamental Research, grant 99-01-01163. Supported in part by the U.S. National Science Foundation under Grant PHY-9970769 and Cooperative Agreement EPS-9720652 that includes matching from the Louisiana Board of Regents Support Fund.