Interpretation of multifrequency transient EPR spectra of the P 700 + A0Q K − state in photosystem I complexes with a sequential correlated radical pair model: Wild type versus A0 mutants

Transient electron paramagnetic resonance (TR-EPR) spectra of the electron-hole pair state P ₇₀₀ ⁺ A₀Q _K ^? in photosystem I are numerically calculated. Parameter variation concerns mainly the exchange integralJ of the precursor spin pair state P ₇₀₀ ⁺ A ₀ ^? Q_K and its lifetime τ. A prominent emissive feature in the high-field region (P ₇₀₀ ⁺ part) of the EPR spectrum turns out to be diminished with increasing lifetime τ of the precursor pair state in the case of positive exchange couplingJ>0 (ferromagnetic type). Correspondingly, the emissive feature becomes more pronounced with increasing lifetime τ in the case of negative exchange couplingJ<0 (antiferromagnetic type). These results can be used to interpret the changes in the pattern observed in TR-EPR spectra comparing wild-type and specific A₀ mutants. The central ligating amino acid residue to the A₀ chlorophyll cofactor is mutated from native methionine (M) to leucine (L) in either the PsaA or the PsaB branch. Changes are observed only for the A-side mutant: M688L(PsaA). They are consistent with the following parameters in the precursor pair P ₇₀₀ ⁺ A ₀ ^? :J≈0.5÷1.0 mT and τ=1.5÷2 ns (as compared to τ～0.05 ns in the wild type).     

Pulse ENDOR studies on the radical pair P 700 +· A 1 ·− and the photoaccumulated quinone acceptor A 1 ·− of photosystem I

The secondary acceptor A₁ of the electron transport chain(s) of photosystem (PS) I is a phylloquinone (vitamin K₁, VK₁). Pulse electron paramagnetic resonance and electron nuclear double resonance (ENDOR) experiments at X-band frequencies were performed on the photoaccumulated acceptor radical A ₁ ^·? and the radical pair state P ₇₀₀ ^·+ A ₁ ^·? in PS I ofThermosynechococcus elongatus. The data obtained were compared with data from the respective radical anion of VK₁ in organic solvents. The unusualg tensor magnitude of A ₁ ^·? is explained by the hydrophobic binding pocket of this radical. The hyperfine couplings and the spin (and charge) density distribution is very different for A ₁ ^.? in PS I and VK ₁ ^·? in frozen alcoholic solution. This is attributed to a rather strong one-sided hydrogen bond to A ₁ ^·? . The presence of a hydrogen bond to A ₁ ^·? has only a minor effect ong. The hyperfine coupling constants of A ₁ ^·? determined from the radical pair spectra deviate only slightly from those derived from photoaccumulated A ₁ ^·? in PS I treated with dithionite at high pH. ENDOR resonances of the proton in a H bond were detected and an estimate of the strength and geometry of this bond to A ₁ ^·? was obtained. The significance of the hydrogen bond and other (hydrophobic) interactions of A₁ with the surrounding are briefly discussed.     

Alteration of the Axial Met Ligand to Electron Acceptor A0 in Photosystem I: Effect on the Generation of P 700 ·+ A 1 ·− Radical Pairs as Studied by W-band Transient EPR

Photosystem I (PS I) mutants from the cyanobacterium Synechocystis sp. PCC 6803 bearing point mutations to the axial ligands of A_0A (M688N_PsaA) and A_0B (M668N_PsaB) were studied by high-field W-band electron paramagnetic resonance (EPR) spectroscopy. It was found that the EPR observables of PS I from the M668N_PsaB mutant were virtual identical to that of the wild type (WT), and are clearly distinct from the M688N_PsaA mutant. In particular, the P ₇₀₀ ^·+ decay kinetics in the M688N_PsaA mutant is significantly slower than in the WT or the M668N_PsaB mutant. The analysis of the out-of-phase electron–electron dipolar electron spin echo envelope modulation shows that in the M668N_PsaB mutant, the estimated distance of 26.0 ± 0.3 Å agrees well with the 25.8 Å distance for the P ₇₀₀ ^·+ A _1A ^·? radical pair measured in the X-ray crystal structure. In the M688N_PsaA mutant, two populations are found with estimated distances of 26.0 ± 0.3 and 25.0 ± 0.3 Å in a ratio of 0.7–0.3, which agree well with the 25.8 Å distance for the P ₇₀₀ ^·+ A _1A ^·? radical pair and the 24.6 Å distance for the P ₇₀₀ ^·+ A _1B ^·? radical pair measured in the X-ray crystal structure. The data confirm that under the experimental conditions employed in this work, which involve dark-adapted samples without the pre-reduction of the iron–sulfur clusters, electron transport in cyanobacterial PS I is asymmetrical at 100 K, with the majority of electron transfer taking place through the A-branch of cofactors.     

Comparative study of the semiempirical three-parameter potential energy functions for diatomic molecules

A comparative study is made of four three-parameter semiempirical potential energy functions for 32 electronic states of diatomic molecules and their ions:n ₂:X¹gS _g ⁺ ,B ³π_g,A ³ gS_u,C ³ _u,B′ ³ gS_u.a ¹ π_g, a′gS _u ^? ,Ω ¹δ_u N ₂ ⁺ :X ² gS _g ^gS +A ² π,C ² gS _u ⁺ ,B ² gS _u ⁺ CO:X¹gS⁺,a ³ π, a′³ gS_u,e ³ gS^?,d ³gD₁,A ¹π CO⁺:X²gS⁺,A ² π,B ²gS⁺ O₂:X³gS _g ^? ,B ³ gS_u,c ¹ gS _u ^? ,b ¹gS _g ^s ,a ¹ δ_g,c ³ δ_u O ₂ ⁺ :X ²π_g,A ² π_g, a¹ π_g,b ⁴ gS _g ^? A program for numerically integrating the radial Schrödinger equation by the Cooley method is worked out. Certain additional units are introduced to conserve computer time. The resulting vibrational levels are compared with the experimental levels for all the electronic states studied. It is concluded on the basis of this analysis that it is not possible to describe equally well all the electronic states of various molecules on the basis of any single three-parameter potential function. A method for choosing a potential function for describing some particular electronic state of a diatomic molecule is proposed.     

Electronic color centers in SrF2-Na crystals

It was shown that optical bleaching of M _A ⁺ color centers at 80 K in SrF₂-Na crystals causes the core of an M _A ⁺ -center to transform into the V _a ⁺ Me ⁺ V _a ⁺ configuration, in which all three point defects are arranged diagnonally in the cube cell. Reirradiation of an optically bleached crystal by x-rays generates F _D centers in it: V _a ⁺ Me ⁺ V _a ⁺ + e ^? → V _a ⁰ Me ⁺ V _a ⁺ ≡ F _D. The F _D → M _A ⁺ transformation in SrF₂-Na crystals proceeds at T = 135 K, in contrast to the F _A → M _A ⁺ transformations, which take place at T > 200 K.     

Structural analysis of three-spin systems of photosystem II by PELDOR

The pulsed electron electron double resonance (PELDOR) pulse sequence is applied to a three-spin system consisting of three radicals (Y _D ^· , Y _Z ^· and Q _A ^? ) generated in spinach PS II. The distance between Y_Z and Q_A has been determined to be 3.4 nm with the previously derived distances of the other radical pairs, 2.9 nm for Y _D ^· -Y _Z ^· and 3.9 nm for Y _D ^· -Q _A ^? . This distance has been derived from the Y _Z ^· -Q _A ^? radical pair trapped in Y_D-less mutants ofChlamydomonas reinhardtii. Furthermore the method was applied to the Y _D ^· -Q _A ^? -Chl _Z ⁺ system to find the unknown distance between Q_A and Chl_Z. The derived distance was 3.4 nm. A triangular configuration was found in the membrane system that gives the relative positions of the electron transfer components.     

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.     

Hyperfeinstruktur und Lebensdauer des 82 P 3/2-Terms von Rubidium

The hyperfine structure splitting of the 8² P _3/2 state of Rb⁸⁵ and Rb⁸⁷ has been investigated with optical double resonance. The following interaction constants have been obtained:A _8p ⁸⁵ =1.99(2) MHz,B _8p ⁸⁵ =1.98(12) MHzA _8p ⁸⁷ =6.75(3) MHz,B _8p ⁸⁷ =0.96(6) MHz. The lifetime of the 8² P _3/2 state is: τ=4.0(8) · 10^?7 sec.     

Lebensdauer- und Hyperfeinstrukturmessungen an einigen angeregten Zuständen der Konfiguration 4d 9 5p im Pd I-Spektrum mit der Level-crossing-Methode

Lifetimes and hfs coupling constants of some excited states of the 4d ⁹ 5p configuration of Pd I have been determined in a level crossing experiment by observing the field dependence of the polarization of the fluorescence radiation in a magnetic field. From the halfwidths of the measured zero field level crossing signals one obtains the mean lifetimes of the following fine structure states:τ(³P ₁ ⁰ )=(7.46±0.32)nsec;τ(³ P ₂ ⁰ )=(6.9±0.76)nsecτ(³P ₁ ⁰ )=(4.99±0.35)nsec;τ(³ D ₁ ⁰ )=(4.89±0.40)nsecτ((³D ₃ ⁰ )=(6.99±0.49)nsec;τ(³ F ₄ ⁰ )=(7.09±0.46)nsec.Δm=2 crossing signals were detected in the³ P ₁ ⁰ ,³D ₃ ⁰ and³F ₄ ⁰ -states of the odd isotope¹⁰⁵Pd. A detailed analysis of the experimental curves yields the hfs coupling constantsA andB of these states:A(³P ₁ ⁰ )=?(133±2) Mc/sec;B(³ P ₁ ⁰ )=(140±30) Mc/secA(³D ₃ ⁰ )=?(120±10) Mc/sec;B(³ D ₃ ⁰ )=?(660±100) Mc/secA(³F ₄ ⁰ )=?(87±2) Mc/sec;B(³ F ₄ ⁰ )=?(330±30) Mc/sec. A theoretical calculation of the hfs constants is given on the basis of reduced matrix elements. Within the limit of the errors these values agree with the experimental ones. The nuclear electric quadrupole moment deduced from the measuredB values isQ (¹⁰⁵Pd)=(0.8±0.3)·10^?24 cm² (without corrections).     

Ab initio calculation of transition dipole moments for transitions between valence states in oxygen molecules

Results of ab initio calculations of potential-energy curves for 20 singlet and 20 triplet valence states of oxygen with configuration interaction taken into account in the 6-31G basis are presented. Transition dipole moments of triplet-triplet (1³Π_g ← B ³Σ _u ^? , 1³Π_g ← A ³Σ _u ⁺ , 1³Π_g ← A′ ³Δ_u, B ³Σ _u ^? ← X ³Σ _g ^? , 2³Π_u ← 1³Π _g, 2³Σ _g ^? ← B ³Σ _u ^? , 1³Π_u ← X ³Σ _g ^? , 2³Π_u ← X ³Σ _g ^? , 2³Π _g ← A′³Δ_u, 3³Π_g ← A′ ³Δ _u, 2³Δ_u ← 2³Π_g, 3³Π_g ← B ³Σ _u ^? , and 2³Π_g ← A ³Σ _u ⁺ ) and singlet-singlet (2¹Σ _g ⁺ ← 2¹Π_u, 2¹Π_u ← 1¹Π ^g, ¹Π_u ← 2¹Δ_g, 1¹Π_g ← c ¹Σ _u ^? , ¹Π_u ← b ¹Σ _g ⁺ , 1¹Δ _u ← a ¹Δ_g, 2¹Π_u ← a ¹Δ_g, 2¹Δ_g ← 1¹Δ_u, ¹Π _u ← a ¹Δ _g, 1¹Π_u ← b ¹Σ _g ⁺ , 2¹Π_g ← 1¹Π_u, 2¹Π _g ← c ¹Σ _u ^? , 1¹Δ _u ← 1¹Π _g, f′Σ _u ⁺ ← b ¹Σ _g ⁺ , 2¹Σ _g ⁺ ← f ′¹Σ _u ⁺ , 3¹Π_g ← 1¹Δ_u) radiative transitions are calculated as functions of internuclear separation. The possibility of observing these transitions under experimental conditions is discussed.     

Hot gluon matter in a constantA 0 background

We compute the effective action of finiteT SU(3) gauge theory in a constant diagonal background fieldA ₀(t,x)=B ₀ ³ T₃+B ₀ ⁸ T₈ in the general covariant background gauge up to terms of orderg ³.B ₀ ^3,8 shield the infrared singularities and the aim is to study whether the minimum of the effective action would determine their values dynamically. We find that the orderg ² term depends explicitly on the gauge fixing parameter ξ. Since the background field screens already at the tree diagram level the interactions of the six non-diagonal gluon fields they do not contribute to the plasmon-likeg ³ term. The two diagonal fieldsA ₀ ³ ,A ₀ ⁸ do, but the electric mass squared they develop will become negative if the background fields are larger than aboutT/g. Hence large background fields make the system unstable.     

Electron-vibrational energy exchange in collisions of electronically excited N2(A 3Σ u + ) molecules with Zn(X 1 S) atoms

The interaction matrix between the N₂ molecule in the X ¹Σ _g ⁺ and A ³Σ _u ⁺ states and the Zn atom in the ¹ S and ³ P states calculated earlier by the asymptotic method was used to find the rate constants for the electron-vibrational energy exchange N₂(A ³Σ _u ⁺ , v) + Zn(¹ S) → N₂(X ¹Σ ₈ ⁺ , v′) + Zn(³ P). The calculations were performed by the transition state method, and the probabilities of transitions between intersecting electron-vibrational terms of the system in motion along the reaction coordinate were determined by the Landau-Zener equation. The calculated electron excitation transfer constants between N₂(A ³Σ _u ⁺ , v = 1, 0) and Zn(¹ S) over the temperature range 300–900 K were on the order of 10^?11?10^?12 cm³/s.     

Interaction of Zn atoms in the 1 S and 3 P states with N2 molecules in the X 1Σ g + and A 3Σ u + states at moderate distances between the atom and molecule

An asymptotic method was used to derive analytical expressions for the matrix elements of interaction between the N₂ molecule in the X ¹Σ _g ⁺ and A ³Σ _u ⁺ electronic states and the Zn atom in the ¹ S and ³ P states. Quadrupole-quadrupole, dispersion, and exchange interactions were taken into consideration. The character of the set of diabatic vibronic potential energy surfaces of the system suggests that the energy transfer in the process N₂(A ³Σ _u ⁺ ) + Zn(¹ S) → N₂(X ¹Σ _g ⁺ ) + Zn(³ P) may prove to be rather effective.     

EPR of a fullerene-molecule-derived paramagnetic center as a mesoscopic conducting object

Discussion of theg-factor value of fullerene is based on the model of itinerant electrons restricted to the surface of the fullerene molecule C₆₀. The Ag shift, i.e., the difference between the experimentalg-factor and theg-factor of free electron Δg = g ? 2.0023 for C ₆₀ ^?1 is negative as for a very small metallic conducting particle.g-factor value is proportional to the interaction between itinerant electrons in the conduction band, thus the Δg is negative for C ₆₀ ^?1 and C ₆₀ ^?3 having less than half filled conduction band, while Δg is positive for C ₆₀ ⁺ where the conduction band is almost filled.     

The effect of air impurities on pure neon luminescence

The luminescence decay curves of the 2p ₁ level of the NeI atom (the transition 3p??[1/2]₀?3s??[1/2] ₁ ^° , ?? = 585.2 nm) and the B ²?? _u ⁺ level of the N ₂ ⁺ molecule (the transition B ²?? _u ⁺ (?? = 0)?X ²?? _g ⁺ (??? = 0), ?? = 391.4 nm) in pure and air-containing neon are measured. The gas was excited by electron beam pulses (E _e = 150 keV, ?? = 5 ns, I _max = 500 A). It is shown that the molecular gases contained in air strongly quench the long-lived component of neon luminescence exciting due to dissociative recombination of Ne ₂ ⁺ molecular ions. The relative light yield at a wavelength of 585.2 nm as a function of the partial pressure of air in neon is determined to be ?? = (1+ 2??p)^?1, where p is the air pressure in Torr.     

Leading/nonleading charm-production asymmetry in Σ− p interactions

The asymmetry between the spectra of leading and nonleading charmed mesons that was measured in Σ^? A interactions at p _L=340 GeV/c in the WA89 experiment is described within the Model of Quark-Gluon Strings (QGS model also known as QGSM) under the assumption that there is a fraction of charmed sea quark-antiquark pairs (intrinsic charm) in an interacting hyperon. It is shown that the asymmetries between D ^?-and D ⁺-meson spectra and between D _s ^? -and D _s ⁺ -meson spectra can be approximated by QGSM curves obtained with the same string-fragmentation parameter, a ₁=10, and the same intrinsic-charm fraction, $\delta _{c,\bar c} = 0.01$ , as those that were used in describing D _s ^? /D _s ⁺ -meson asymmetry of π^? A experiments in previous studies. The asymmetry between the spectra of Λ_c and $\bar \Lambda _c $ that was measured in Σ^? A collisions at p _L=600 GeV/c in the E781 experiment is also described within this scheme. The QGSM results are compared with the results of the calculations in the next-to-leading approximation of perturbative QCD that were performed by other authors.     

E2 andE3 transition strengths in some rare-earth nuclei

Coulomb excitation byα-particles of vibrational-like states in even-mass rare-earth nuclei is used to determine the reduced transition probabilitiesB(E2; 0 _gs ⁺ →2 _γ ⁺ ),B(E2; 0 _gs ⁺ →2 _β ⁺ ),B(E2; 2 _gs ⁺ →0 _β ⁺ ) andB(E2; 0 _gs ⁺ →3 _oct ^? ) in¹⁵⁰Nd,^{152, 154}Sm,^{154, 158}Gd,¹⁶⁴Dy and¹⁶⁶Er. TheB(Eλ; 0 _gs ⁺ →I=λ)-values range from 2.4 to 6.5 single-particle units for transitions to the 2 _γ ⁺ -states, 0.8 single-particle units for the 2 _β ⁺ -states and from 14.1 to 21.7 single-particle units for the 3^?-states.     

Comparison of electron spin polarization of P 870 + Qa a − observed in Zn2+-containing and Fe2+-depleted bacterial reaction centers

Recently, a general model has been developed to explain electron spin polarized (ESP) electron paramagnetic resonance (EPR) signals found in systems where radical pairs are formed sequentially. The photosynthetic bacterial reaction center (RC) is such a system in which we can experimentally vary parameters (lifetime, structure, and magnetic interactions in the sequentially formed radical pairs) that affect ESP development in order to test this model. In Fe²⁺-depleted transfer step from intermediate radical pair, P ₈₇₀ ⁺ Q _a ^? which is produced in an electron transfer step from intermediate radical pair, P ₈₇₀ ⁺ I^?. (P ₈₇₀ ⁺ is the oxidized primary donor, a special pair of bacteriochlorophyll molecules, I^? is the reduced bacteriopheophytin acceptor, and Q _a ^? is the reduced primary quinone acceptor.) The lifetime of P ₈₇₀ ⁺ I^? can be shortened relative to the lifetime of P ₈₇₀ ⁺ I^? in Fe²⁺-depleted RCs by substitution of Zn²⁺. We report the first observation of X-band and Q-band ESP EPR signals due to P ₈₇₀ ⁺ Q^? from bacterial reaction centers that contain Zn²⁺. Comparison of these signals to those observed from Fe²⁺-depleted bacterial reaction centers shows intensity differences and g-factor shifts. The results are discussed in terms of the general sequential radical pair model.     

Electron spin polarization in consecutive spin-correlated radical Pairs: Application to short-lived and long-lived precursors in type 1 photosynthetic reaction centres

An analytical treatment of the spin dynamics in sequential photoinduced correlated coupled radical pairs is presented and applied to the spectra of the states P⁺A ₁ ^? and P⁺F _x ^? in type 1 photo-synthetic reaction centres. Expressions for the spin polarized spectra are derived for the specific limiting cases of a very short-lived and very long-lived primary radical pair which correspond to the situation found in heliobacteria and photosystem I (PSI), respectively. The inhomogeneous line-broadening due to the unresolved hyperfine couplings is taken explicitly into account. It is shown that the density matrix of the secondary pair ρ₂ can be written as the sum of two terms corresponding to (i) the part which is independent of the spin dynamics in the precursor, (ii) the additional spin polarization which is generated during the lifetime of the precursor and transferred to the secondary pair. The latter term contains two contributions which arise from the difference of the Zeeman interactions of the radicals in the primary pair and from the inhomogeneous line broadening. The predicted polarization patterns are compared to those established for chemically induced dynamic electron polarization (CIDEP) when uncoupled radicals are generated from a radical pair precursor. The expressions are then used to simulate the experimental spectra of the consecutive pairs P⁺A ₁ ^? and P⁺F _x ^? in PSI using parameters derived entirely from independent experimental data. Excellent agreement with the experimental results is obtained. The spectra of P⁺F _x ^? in heliobacteria at X- and K-band are also simulated and it is shown that the observed polarization patterns can be reproduced assuming direct electron transfer from A₀ to F_x with a time constant ofτ = 600 ps.     

EPR studies on the di-nitrogen centers with nonequivalent atoms in a reddish-brown plastically deformed diamond

Two new di-nitrogen centers, which were labeled M2 and M3, were found together with known W7 and N4 centers in an unusual reddish-brown natural diamond. The following magnetic hyperfine interaction parameters (expressed in MHz) were determined for the two nitrogen atoms:A ₁ ⁽¹⁾ =117.95(5),A ₁ ⁽²⁾ =A ₁ ⁽³⁾ =84.48(5),A ₂ ⁽¹⁾ =7.1(1),A ₂ ⁽²⁾ =A ₂ ⁽³⁾ =6.6(1) for M2 andA ₁ ⁽¹⁾ =121.55(5),A ₁ ⁽²⁾ =A ₁ ⁽³⁾ =85.90(5),A ₂ ⁽¹⁾ =6.0(1),A ₂ ⁽²⁾ =5.4(1),A ₂ ⁽³⁾ =5.1(1) for M3. Hyperfine interaction tensors for the nitrogen atom N₁ with a larger interaction have axial symmetry about the <111> direction, but those for the other nitrogen atom, N₂, appear to be small, almost isotropic. Probable models of the M2 and M3 centers are suggested and discussed.