Manifestation of nonplanarity effects and charge-transfer interactions in spectral and kinetic properties of triplet states of sterically strained octaethylporphyrins

Properties of the triplet states of octaethylporphyrins with the steric hindrance (free bases and Pd complexes) are studied by the methods of stationary and kinetic spectroscopy in the temperature range from 77 to 293 K. The mono-mesophenyl substitution results in a decrease in the quantum yield and shortening of the phosphorescence lifetime of Pd complexes by 250–3500 times in degassed toluene at 293 K. The phosphorescence quenching is caused by nonplanar dynamic conformations of the porphyrin macrocycle in the T ₁ state, which also lead to the appearance of new bands at λ～1000 nm in the T-T absorption spectra. As the number of meso-phenyls (Pd-octaetyltetraphenylporphyrin) increases, the quantum yield of phosphorescence further decreases (<10^?5) at 293 K, the lifetime of the T ₁ state shortens (<50 ns), and the efficiency of the singlet oxygen generation abruptly decreases (<0.01). The intense bathochromic emission of this compound at 705 nm with a lifetime of 1 ms at 77 K is assigned to the phosphorescence of a nonplanar conformation. Upon meso-orthonitrophenyl substitution, the quenching of phosphorescence of Pd complexes (by more than 10⁴ times at 293 K) is caused by direct nonadiabatic photoinduced electron transfer from the T ₁ state to the nearest charge-transfer state with the probability k _et ^T =(1.5–4.0)×10⁶ s^?1. The induced absorption of ortho-nitro derivatives in the region between 110 and 1400 nm is caused by mixing of pure ππ* states with charge-transfer states.     

Neutrino-induced deuteron disintegration in an experiment at the Krasnoyarsk nuclear reactor

The results of studying antineutrino interactions with deuterons (CCD and NCD reactions) and hydrogen (CCP) at the Krasnoyarsk underground reactor with the Deuteron detector are presented. The cross sections for NCD and CCD were measured with a precision of 9%. For CCP, the precision is 3%: σ _expt ^NCD =(3.35±0.31)×10^?44 cm²/fission ²³⁵U, σ _expt ^NCD =(1.08±0.09)×10^?44 cm²/fission ²³⁵U, and σ _expt ^NCD =(6.39±0.19)×10^?43 cm²/fission ²³⁵U. The precision of the experimental results is close to the theoretical one and is in good agreement with other experiments. The limit on the parameters of antineutrino oscillations into the sterile state was obtained: Δm ²≤4.7×10^?2 eV² for sin²(2?)=1.0 (68% C.L.). A comparison of the measured and theoretical cross section gives us the neutron-neutron scattering length of a _nn(S)=?17±6 fm in the approach of zero momentum transfers. The weak neutral current constant is in good agreement with the prediction of the Standard Model: G _A ^NC =G _A ^CC /0.932±0.056.     

Astrophysical S factor for dd interaction at ultralow energies

Experimental results are presented that were obtained by measuring the astrophysical S factor for dd interaction at very low deuteron collision energies by using the liner-plasma technique. The experiment was performed at the high-current generator of the High-Current Electronics Institute (Tomsk, Russia). The values found for the S factor at the deuteron collision energies of 1.80, 2.06, and 2.27 keV are S _dd=114±68, 64±30, and 53±16 keV b, respectively. The corresponding dd cross sections obtained as the product of the barrier factor and the measured astrophysical S factor are σ _dd ⁿ (E _col=1.80 keV)=(4.3±2.6)×10^?33cm², σ _dd ⁿ (E _col=2.06 keV)=(9.8±4.6)×10^?33cm², and σ _dd ⁿ (E _col=2.27 keV)=(2.1±0.6)×10^?32cm².     

Untersuchung der vier ersten angeregten Zustände des6Li-Kernes durch Elektronenstreuung

Inelastic electron scattering cross sections were measured for energies below 60 MeV and momentum transfersq between 0.2 and 0.6 fm^?1. Ground state radiative widths Γ _γ ⁰ and transition radiiR _tr were deduced. 2.18 MeV: Γ _γ ⁰ (E2)=(4.40±0.34) · 10^?4 eV,R _tr=(4.28±0.39)fm; 3.56MeV: Γ _γ ⁰ (M1)=(8.31±0.36)eV,R _tr=(2.90±0.10)fm; 4.27 MeV: Γ _γ ⁰ (E2)=(5.4±2.8) · 10^?3 eV,R _tr=(3.4±1.2) fm. The excitation of the 5.37 MeV level shows a transverse angular dependence.     

Roles played by an oxygen atom and out-of-plane high-frequency vibrational modes of a dibenzofuran molecule in the nonradiative deactivation of the lowest triplet state

We have studied the deactivation of the triplet sublevels s = z, y, and x of the lowest triplet state T ₁ ^s of the dibenzofuran molecule, which is determined by radiative (dipole) and nonradiative (degradation) transitions with the rate constants K _rad ^s and K _dg ^s . The main attention is paid to the nonradiative transitions T ₁ ^s ? S ₀ from the in-plane spin states (s = z, y), which are determined by the intramolecular interaction along the coordinates of out-of-plane vibrational modes. The roles played by the many-electron atom (oxygen) and high-frequency out-of-plane vibrational modes in the intramolecular interaction have been evaluated theoretically. Estimates of K _dg ^s based on three known approaches (three models) that describe the nonradiative transition in the approximation of adiabatic and nonadiabatic interactions are presented.     

Observation of perturbations in the rovibronic transition probabilities for the (4d)r 3Π g − , (4d) s 3 Δ g − → (2p) c 3Π u ± band systems of the H2 molecule

The ratios of the radiative transition probabilities for the lines of the P, Q, and R branches of the (4d)r ³Π _g ^? , (4d)s ³Δ _g ^? → (2p) c ³Π _u ^± band systems of the H₂ molecule have been measured for the first time. Significant (to two orders of magnitudes) differences are found between the experimental values and the adiabatic theory predictions. It is established that the results of the nonadiabatic calculation performed by us in the pure-precession approximation taking into account the electronic-rotational interaction of the 4d ³Π_g and 4d ³Δ_g states are in agreement with the experimental data. The optimal energies of rovibronic levels of the r ³Π _g ^? , s ³Δ _g ^? , c ³Π _u ^? , and c ³Π _u ⁺ states have been found and reidentification of 11 from 54 spectral lines, assigned previously to the (0-0) and (1-1) bands, was performed.     

Inclusive production ofK s 0 , K s 0 K s 0 andK *±(892) in\bar pp interactions at 3.0, 3.5, 4.0 and 4.5 GeV/c

InclusiveK _s ⁰ andK _s ⁰ K _s ⁰ production in \(\bar pp\) interactions at 3.0, 3.5, 4.0 and 4.5 GeV/c are studied. Cross sections ofK _s ⁰ , K _s ⁰ K _s ⁰ andK ^*±(892) are presented for each incident momentum. The production ofK _s ⁰ andK ^*±(892) through annihilation process is investigated. It is found that the annihilation process is dominant but decreases with incident momentum. The annihilation process is compared withe ⁺ e ^? interactions. Remarkable similarity between them is found in the \({{x_0 = 2E(K_s^0 )} \mathord{\left/ {\vphantom {{x_0 = 2E(K_s^0 )} {\sqrt s }}} \right. \kern-0em} {\sqrt s }}\) distribution. Events with two detectedK _s ⁰ 's are analyzed. The result shows theK _s ⁰ K _s ⁰ pairs are produced in the central region of c.m. system and there is a clearS ^* signal in theK _s ⁰ K _s ⁰ effective mass distribution.     

Temperature dependence of Mn2+ EPR in Sn2P2S6 near the phase transition

The X-band EPR spectrum of Mn²⁺ in Sn₂P₂S₆ was studied in the temperature rangeT=223–363 K. At room temperature the spin-Hamiltonian constants areg=2.00±0.01,B ₂ ⁰ =(163±3)·10^?4 cm^?1,B ₂ ² =(159±3)·10^?4 cm^?1,A=?(75±1)·10^?4 cm^?1. The effect of the invariance in temperature of the resonance magnetic fields in the narrow temperature rangeT=337–340 K and the model of the paramagnetic centre are discussed. According to EPR data a phase transition occurs atT=337 K. This transition from the paraelectric phase to the ferroelectric one is accompanied by a dramatic change in value of the spin-Hamiltonian constantB ₂ ⁰ .     

Nonradiative deactivation of the lowest triplet state of tetrachlorodibenzo-p-dioxin

In the nonadiabatic approximation, we have studied how the shape of promoting out-of-plane vibrational modes and vibronically induced spin-orbit interactions in structural elements of the 2,3,7,8-tetrachlorodibenzo-p-dioxin molecule affect the energy degradation rate constants K _dg ^s of triplet T ₁ ^s sublevels.     

Study of B s 0 → µ+µ− and B d 0 → µ+µ− decays in flavor-changing Z′ models

Recently, the first evidence for the decay B _s ⁰ → μ ⁺ μ ^? has been announced by the LHCb Collaboration and the measured branching ratio B( _s ⁰ → μ ⁺) = (3.2 _?1.2 ^+1.5 ) × 10^?9 is in good agreement with the standard model (SM) expectation. It has also reported an upper limit for B(B _d ⁰ → μ ⁺ μ ^?) < 9.4 × 10^?10 at 95% confidence level. In this paper, we study the B _s ⁰ → μ ⁺ μ ^? and B _d ⁰ → μ ⁺ μ ^? rare decays in flavor-changing Z′ model. Our estimated branching ratios are enhanced from their SM values and provide signals for new physics.     

Determination of the ππ scattering lengths from data on πN → ππN reactions by the method of Roy equations

Fitted phase-shift curves from the threshold to the dipion mass, which is equal to 1 GeV, are constructed on the basis of all available experimental values of the S-and P-wave phase shifts for five charged channels of pion-pion scattering. The resulting phase-shift curves are introduced in the Roy equations in order to obtain the subtraction constants λ _l ^I (s). By using these subtraction-constant values as functions of the dipion mass, the S ₀-and S ₂-wave pion-pion scattering lengths are found to be a ₀ ⁰ = (0.240 ± 0.023)m _π ^?1 and a ₀ ² = (?0.034 ± 0.013)m _π ^?1 . A strong correlation of the S-wave scattering lengths is demonstrated.     

Hadronic contributions to (g−2) of the leptons and to the effective fine structure constant α(M Z 2 )

The new experiment planned at Brookhaven to measure the anomalous magnetic moment of the muona _μ≡(g _μ?2)/2 will improve the present accuracy of 7 ppm by about a factor of 20. This requires a careful reconsideration of the theoretical uncertainties of theg?2 predictions, which are dominated by the error of the contribution from the light quarks to the photon vacuum polarization. This issue is cruicial also for the precise determination of the running fine structure constant at theZ-peak as LEP/SLC experiments continue to increase their precision. In this paper we present an updated analysis of the hadronic vacuum polarization using all presently availablee ⁺e^? data. This seems to be justified because previous work on the subject was based to some extent on preliminary or incomplete experimental data. Contributions from different energy ranges are presented separately forg?2 of the muon and the τ-lepton and for α(M _Z ² ). We obtain the resultsa _μ ^had* =(725±16)×10^?10 anda _τ ^had* =(351±10)×10^?8, where the asterisk indicates the dressed (renormalization group improved) value. For the effective fine structure constant atM _Z=91.1888 GeV we obtainΔα _had ⁽⁵⁾ =0.0280±0.0007 and α(M _Z ² )^?1=128.896±0.090. Further improvement in the accuracy of theoretical predictions which depend on the hadronic vacuum polarization requires more precise measurements ofe ⁺e^? cross-sections at energies below about 12 GeV in future experiments.     

Correlation femtoscopy of Kaons in the SELEX experiment

Preliminary results from the correlation femtoscopy of identical kaons in the SELEX experiment (Fermilab E781) are presented. Kaons are selected in inclusive reactions of Σ^?C(Cu) interactions at an initial energy of 610 GeV. Kaon pairs are studied in all possible charged states: K _s ⁰ K _s ⁰ , K _s ⁰ K⁺, K _s ⁰ K^?, K⁺K⁺, K⁺K^? and K^?K^?. The source sizes of the hadronization region of neutral and charged kaon pairs are measured.     

Semiempirical investigation of perturbations of the g factors of electronic-vibrational-rotational levels of hydrogen: III. The r 3Π g − and s 3Δ g − states of the H2 and D2 molecules

The g factors of rovibrational levels of the (4d)r ³Π _g ^? and (4d)s ³Δ _g ^? states of the H₂ and D₂ molecules have been obtained for the first time. These values were found within the nonadiabatic model taking into account the interaction of the 4dπ³Π_g and 4dδ³Δ_g states in the pure precession approximation using semiempirical values of the expansion coefficients of the wave function in an adiabatic basis, which was obtained for the first time for the states of the triplet 4d complex of terms of the hydrogen molecules, and the results of numerical calculation of the overlap integrals of the vibrational wave functions of these states. It is established that the interference effects of the interaction between the 4dπ³Π _g ^? and 4dδ³Δ _g ^? states lead to significant (up to 7 times for the r ³Π _g ^? state of the H₂ and D₂ molecules and 70 and 8 times for the s ³Δ _g ^? state of the H₂ and D₂ molecules, respectively) differences between the nonadiabatic values of the g factors and the corresponding adiabatic values. It is found that the perturbed values of the g factors are much closer to the values corresponding to the case of Hund’s d coupling of angular momenta than to the values corresponding to the b coupling. It is established that the perturbations of the g factors of rovibrational levels of the states of the 4d complex of terms are much greater (up to 2 times for the ³Π _g ^? states and 350 times for the ³Δ _g ^? states) than the perturbations of the same characteristics for the 3d complex of terms of the hydrogen molecule with the same vibrational and rotational quantum numbers.     

Electron-electron interaction and instabilities in one-dimensional metals

The possible instabilities of a 1-dimensional itinerant electron gas are discussed, assuming electron-electron interaction to play the dominant role. As is well known, in the RPA, a 1-dimensional metal is prone to spin density wave (SDW), charge density wave (CDW) and Cooper pair (CP) instabilities. The spin channel decomposition of the irreducible scattering amplitude I is made and the spin channel projections are evaluated in terms of the matrix elements of bare electron-electron interactionV(x) for momenta of interest. It is found that if the bare electron interactionV(x) is repulsive and decreases monotonically with separation, only the SDW instability will occur. If the small separation (x?(2k _F )^?1) part of the interaction is greatly reduced or is made attractive,V(x) is non-monotonic,V _q (q?2k _F ) is negative, and a CDW instability is preferred. A CP instability is possible if the electron interaction is attractive,i.e., if [V _q (0<q<k _F )+V _q (q?2k _F )]<0. The above RPA results serve only as rough indicators, since in general there are important two-electron configurations with two-electron momentum close to zero and with electron hole momentum close to 2k _F , an example being the near Fermi energy configurationk ₁?k _F ,k ₂??k _F ,k ₃??k _F k ₄?k _F . Therefore as pointed out first by Bychkov, Gorkov and Dzhyaloshinskii (BGD), cross channel coupling is especially significant. It is shown that the cross channel coupling is constructive is some cases,eg., exchange of CD fluctuations leads to an effective electron-electron spin singlet attraction and vice-versa. A formalism for studying such effects is set up, and the particular example mentioned above is discussed. An RPA-like approximation is made for the form of the reducible singlet electron hole scattering amplitudeγ _s ^d and the resulting induced Cooper pair attraction is calculated to be $$\begin{gathered} [I_s ^e ]_{ind.} \rho _{{}^\varepsilon F} = [ln(\lambda \beta \omega _c )]^{ - 1} ln\{ [1 + 2\pi ^{ - 1} ln(\lambda \beta \omega _c )^2 ]/ \hfill \\ 1 + [8\pi ^{ - 1} \gamma _s ^d (q = 2k_F )^{ - 1} )^2 ]\} \hfill \\ \end{gathered} $$ where λ=1.14,β=(k _B T)^?1 andω ₀ is an electronic energy cut-off ～ε _F . The induced electron hole attraction due to the exchange of virtual Cooper pairs has a similar expression, but with a factor of (1/4) and withγ _s ^e (q=0) replacingγ _s ^d (q=2k _F ). The induced Cooper pair attraction is seen to be quite large over a broad range of temperatures close to but aboveT _CDW [i.e., aboveT such thatγ _s ^d (q=2k _F )^?1=0]. There is no requirement thatγ _s ^d (q=2k _F ) andγ _s ^e (q=0) become singular at the same temperature, as found by BGD. The BGD prediction is seen to arise from the neglect of real particle hole and particle-particle excitations while calculatingγ _s ^d andγ _s ^e . The effect of impurities, of electron-phonon coupling, of interchain coupling and of interaction between thermal order parameter fluctuations is discussed. The results are then applied to a discussion of the properties of TTF-TCNQ, where it is suggested that a CDW instability occurs becauseV _q (q=2k _F )<0,i.e., because the small separation electron repulsion is strongly reduced by the highly polarizable TTF. Because of substantial interchain coupling, the bulk CDW instability occurs close to the RPA instability temperature. The giant conductivity observed by Colemanet al is attributed to superconductive fluctuations in a 1-dimensional system with large mean field superconductive transition temperatureT _CP ^MF of order 300°K. Such a largeT _CP ^MF is shown to result from the induced Cooper pair attraction due to CD fluctuation exchange.     

Pionic deuterium

The strong-interaction shift ε _1s ^πD and broadening Γ _1s ^πD in pionic deuterium have been determined in a high statistics study of the πD(3p-1s) X-ray transition using a high-resolution crystal spectrometer. The pionic deuterium shift will provide constraints for the pion-nucleon isospin scattering lengths extracted from measurements of shift and broadening in pionic hydrogen. The hadronic broadening is related to pion absorption and production at threshold. The results are ε _1s ^πD = (?2356 ± 31) meV (repulsive) and Γ _1s ^πD meV yielding for the complex πD scattering length a _πD = [?(24.99±0.33)+i(6.22 _?0.26 ^+0.12 )] × 10^?3 m _π ^?1 . From the imaginary part, the threshold parameter for pion production is obtained to be α = (251 _?11 ⁺⁵ ) μb. This allows, in addition, and by using results from pion absorption in ³He at threshold, the determination of the effective couplings g ₀ and g ₁ for s-wave pion absorption on isoscalar and isovector NN pairs.     

Analysis of average primary gamma-transition intensities and cross sections of the113Cd(n, γ) reaction

A combined analysis of the available data on the primaryγ-ray intensities from the¹¹³Cd(n, γ) reaction atE _n=1.9 and 24.3 keV neutron energies together with the data on¹¹³Cd neutron capture cross sections in theE _n=3–200 keV energy region was carried out. The neutron strength functions were determined asS _n0=(0.260±0.073) 10^?4 and S_n1=(5.06±0.67) 10^?4. No spin-orbit splitting of thep-wave neutron strength function was found. The energy dependence of theE 1 radiative strength function {ie147-01} was fitted by the Kadmenski-Furman model somewhat better than by a standard Lorentzian. TheM 1 giant resonance parameters were obtained as E _G ^{M 1} =8.8±1.6 MeV and Γ _G ^{M 1} = 4.7±2.6 MeV. The neutron capture cross section of¹¹³Cd from its isomeric state ({ie147-02}=11/2^?, E ₁ ^m =263.7 keV) was calculated.     

Diffractive production of charmed strange mesons by neutrinos and antineutrinos

The diffractive production of charmed strangeD _s ^* and possiblyD _s mesons by neutrinos and antineutrinos on nucleons in hydrogen, deuterium and neon targets is observed. The slope parameter of thet distribution is 3.3±0.8 (GeV)^?2. The production rate per charged current neutrino interaction with an isoscalar target times the D _s ⁺ →φτ⁺ branching fraction is (1.03±0.27)×10^?4.     

Changes in metal specificity due to iron ligand substitutions in reaction centers fromRhodobacter sphaeroides

Bacterial reaction centers have a single nonheme iron that is located between two bound quinones, Q_A and Q_B, which are the primary and secondary electron acceptors during photosynthesis, respectively. InRhodobacter sphaeroides, the iron is coordinated by four nitrogen atoms, contributed by histidines at L190, L230, M219, and M266, and two oxygen atoms, contributed by Glu at M234. The roles of these ligands in determining the metal-binding specificity and electron transfer properties of the quinones were investigated by mutagenesis. Each of the four His ligands was changed to Glu, Gln, and Cys, whereas Glu was changed to His, Gln, Cys, and Asp. All mutants supported photosynthetic growth except for those with substitutions of Glu or Cys at L190 or M219. The metal specificity of isolated mutant RCs was determined by measurements using atomic absorption and 35 GHz electron paramagnetic resonance spectroscopy. The M234 mutants had a lesser iron specificity than the wild type with a mole fraction of 0.7 to 0.8 iron but retained a total metal content of 1.0. All His mutants had an even lower iron content with mole fractions of 0.04 to 0.16. The His to Cys at M266 mutant had a significantly greater amount of bound zinc that was further enhanced when the strain was grown in zinc-supplemented media. The charge recombination rates from Q _B ^?. , which ranged from 0.5 to 1 s^?1 in the mutants, were comparable to the 1 s^?1 value for the wild type. Charge recombination from Q _A ^?. showed complex kinetics, with rates of 15 to 30 s^?1 for the L190, L230, and M234 mutants and 200 s^?1 for the M266 mutants compared with 8 s^?1 for the wild type. The faster rates in the mutants most likely reflected a smaller free energy difference between Q _A ^?. and Φ _A ^? , a nearby bacteriopheophytin, with the smaller energy difference facilitating indirect recombination. All of the mutants transferred electrons to the secondary quinone, with rates (1200 to 4700 s^?1) comparable to that of the native (3700 s^?1). The data demonstrate that neither the ligands nor the bound metal play a critical role in the electron transfer processes at the acceptor side.     

Effects of final-state interactions in pure annihilation decay of B s 0 → π+π −

The hadronic decay of B _s ⁰ → π ⁺ π ^? is analyzed by using “QCD factorization” (QCDF) method and final-state interaction (FSI). First, the B _s ⁰ → π ⁺ π ^? decay is calculated via QCDF method and the annihilation graphs only exist in this method. Hence, the FSI must be seriously considered to solve the B _s ⁰ → π ⁺ π ^? decay and the K ^+(*) K ^?(*) and \(K^{0(*)} K^{\bar 0(*)}\) via the exchange of K ^0(*) and K ^?(*) mesons are chosen for the intermediate states. To estimate the intermediate state amplitudes, the QCDF method is again used. These amplitudes are used in the absorptive part of the diagrams. The experimental branching ratio of B _s ⁰ → π ⁺ π ^? decay is less than 1.2 × 10^?6 and our results according to the QCDF method and FSI are 0.68 × 10^?8 and 1.18 × 10^?6, respectively.