Mechanism by which a single water molecule affects primary charge separation kinetics in a bacterial photosynthetic reaction center of Rhodobacter sphaeroides

Using quantum-chemical methods, we have studied the role played by water molecules W-A and W-B that are bound by hydrogen bonds to accessory bacteriochlorophyll molecules B _A and B _B in the process of primary charge separation in the reaction center of Rhodobacter Sphaeroides. We have found that the occurrence of a rotational mode of the W-A molecule at 32 cm^?1 and/or its harmonics in stimulated emission of an electron donor P* and the dynamics of population of the states P⁺B _A ^? and P⁺H _A ^? may be related to the structural heterogeneity of the reaction center and the existence of a conformation in which the W-A molecule is predominantly involved in one hydrogen bond (with BA). Based on the calculated redox potentials B _A and P, it has been shown that the appearance of the W-A molecule in the reaction center reduces the energy of the P⁺B _A ^? state by ??600 cm^?1. This is somewhat smaller than the influence of the amino-acid residue Tyr^M210 (??870 cm^?1) and correlates well with a substantial decrease in the electron transfer rate in mutant forms of reaction centers GM203L (which do not contain W-A molecules) and YM210F (in which Tyr^M210 is replaced with Phe). The data obtained allow us to suggest that rotation of the water molecule with a fixed position of its H atom that is involved in a hydrogen bond with the keto carbonyl group of B _A is initiated due to the charge separation between the halves of special pair P and the formation of the state P _A ⁺ P _B ^? . The large effect of this rotation on the kinetics of population of the states P⁺B _A ^? and P⁺H _A ^? after the excitation of P is quite consistent with its influence on the energy of the state P⁺B _A ^? .     

Theoretical study of molecular properties of low-lying electronic excited states of H2O and H2S

Geometries, excitation energies, dipole moments and dipole polarisability tensor components of the ground and four lowest excited states ³ B ₁, ¹ B ₁, ³ A ₂, ¹ A ₂ of the H₂O and H₂S molecules were calculated at the CASSCF, CASPT2, CCSD and CCSD(T) level of approximation. Vertical excitation and equilibrium transition energies of these states, having the Rydberg character, are reported too. Properties of both molecules in the ground and in low lying excited states are compared and discussed from the point of view of their molecular electronic structure. Upon excitation we observe dramatic changes of dipole moments and polarisabilities with respect to the ground state. We stress the change of the polarity of H₂O in all excited states accompanied by the enhancement of the dipole polarisability by an order of magnitude. Large, even if less pronounced, are changes of electric properties of H₂S in its excited states. Dipole moments and dipole polarisabilities of ³ B ₁, ¹ B ₁ states of H₂S and H₂O behave quite analogously in comparison to their respective ground state. The general pattern of properties for both molecules in their ³ A ₂ and ¹ A ₂ excited states is more different due to a pronounced participation of the sulphur d-orbitals in these states of the H₂S molecule.     

The nature of the lower excited state of the special pair of bacterial photosynthetic reaction center of <Emphasis Type="Italic">Rhodobacter Sphaeroides</Emphasis> and the dynamics of primary charge separation

Quantum-chemical calculations of the structure in the ground and lower singlet excited states and the vibrations (in the ground state) of special pair P of photosynthetic reaction center of purple bacteria (RCPb) Rhodobacter Sphaeroides, consisting of two bacteriochlorophyll molecules P_A and P_B, have been carried out. It is shown that excitation of the special pair is followed by fast relaxation dynamics, accompanied by the transformation of the initial P* state into the P_A^δ+P_B^δ- state (δ ~ 0.5) with charge separation. This behavior is due to the presence of several nonplanar vibrations with participation of the acetyl group of macrocycle P_В in the nuclear wave packet on the potential surface of the P* state; these vibrations facilitate destabilization of the lowest unoccupied molecular orbital (LUMO) and highest occupied molecular orbital (HOMO) of the macrocycle P_A and formation of the P_A^δ+P_B^δ- state. The structural transformations in the P* state are due to its linking character in the contact region of the acetyl group-containing pyrrole rings of P_A and P_B. The transition from the P* state to specifically the P_A^δ+P_B^δ- state is related to the fact that the acetyl group P_A is involved in the intermolecular hydrogen bond with amino acid residue His^L168; for this reason, this group and the pyrrole ring linked with it can hardly participate in structural transformations. The electronic matrix element Н₁₂ of the electron transfer from the special pair in the P_A^δ+P_B^δ- state to a molecule of accessory bacteriochlorophyll В_А greatly exceeds that for the transfer to В_B. This circumstance and the fact that the P_A^δ+P_B^δ- state is energetically more favorable than the P* state facilitate the preferred directionality of the electron transfer in RCPb Rhodobacter Sphaeroides with participation of the cofactors located in its subunit L.     

The spectrum of allene near 5 μm

The infrared bands of allene between 1920 and 2028 cm^?1 were measured on a large grating spectrometer with effective resolution of 0.006–0.007 cm^?1 after deconvolution. The main band in this region is the antisymmetric CC stretching fundamental ν₆ of symmetry B₂, accompanied on the high-frequency side by the overtone band 2ν₉ of the degenerate CH₂ rocking vibration. The overtone has three components of species B₂, B₁, and A₁, of which B₂ is in Fermi resonance with ν₆, B₁ has second-order Coriolis interaction with ν₆, while A₁ is in l-type interaction with the B₁ and B₂ components. Additional perturbations by other unobserved states were detected in the spectrum. The observed transitions were analyzed with the aid of a general computer program system SYMTOP designed for analysis of symmetric-top spectra. The main program effects a least-squares refinement of the spectroscopic constants for a set of bands whose upper states interact through arbitrary matrix elements. Two sets of spectroscopic constants for the ν₆, 2ν₉ states were calculated. One, based only on those lines which appear to be unperturbed by unknown and unobserved states, and a second, obtained after inclusion in the H matrix of two perturbing states designed to simulate the effect of the perturbations on all of the data. Comparison indicates that the lower-order constants based merely on the “unperturbed” data are quite satisfactory. Molecular constants for the ν₉ vibration of C₃H₄ are reported.     

Stress-optical studies of VI B transition metal dichalcogenides

The effect of a uniaxial stress on the excitonic optical spectra are studied for MoS₂, WS₂, MoSe₂ and WSe₂. Stress dichroism appears in the A′, B′ excitons in diselenides, while it is absent in the A, B excitons in the four compounds. The A′, B′ excitons shift oppositely to the A, B excitons, indicating that A, B and A′, B′ are not pair excitons split by interlayer interaction.     

Spin-orbit coupling and dissociation of CO2 molecules

Potential surfaces of the CO₂ molecule for the ground and excited ³ B ₂, ¹ B ₂ electronic states are calculated by quantum chemistry methods. The calculation of the spin-orbit coupling in the molecule shows a large the matrix element, which removes the prohibition for the dissociation-recombination process CO₂(X ¹Σ) + M ? CO(X ¹Σ) + O(³ P) + M. The barrier on the potential curve for ³ B ₂, the energy of which exceeds the limit of dissociation into components in the ground states, explains the data on the dissociation and recombination energies measured in experiments with shock tubes. The absorption cross section of CO₂ molecules in the UV spectral region measured at high temperatures allowed us to plot branches of potential curves near their minima for two upper singlet states assigned to the ¹ B ₂ and ¹ A ₂ symmetry.     

Rotational distribution in simultaneously excited electronic states of CH

A²Δ, B²Σ^? and C²Σ⁺ states of CH were excited in discharges through flowing C₂H₂ and C₂H₄ and in flames of C₂H₂. The rotational distributions in these states were determined from the measured integrated intensities of rotational lines for bands of A²Δ → X²Π, B²Σ^? → X²Π and C²Σ⁺ → X²Π. The A²Δ state exhibits a non-Maxwellian distribution while the B²Σ^? and C²Σ⁺ states show Maxwellian distributions. The non-Maxwellian distribution of the A²Δ state and the different rotational distributions in the three states are discussed.     

The Surface Metal Site in Blc. viridis Photosynthetic Bacterial Reaction Centers: Cu2+ as a Probe of Structure, Location, and Flexibility

Metal ion binding to a surface site on photosynthetic reaction centers (RCs) modulates light-induced electron and proton transfer events in the RC. Whereas many studies have elucidated aspects of metal ion modulation events in Rhodobacter sphaeroides RCs, much less is understood about the surface site in Blastochloris viridis (Blc. viridis) RCs. Interestingly, electron paramagnetic resonance studies revealed two spectroscopically distinct Cu²⁺ surface site environments in Blc. viridis RCs. Herein, Cu²⁺ has been used to spectroscopically probe the structure of these Cu²⁺ site(s) in response to freezing conditions, temperature, and charge separation. One Cu²⁺ environment in Blc. viridis RCs, termed Cu_A, exhibits temperature-dependent conformational flexibility. Different conformation states of the Cu_A²⁺ site are trapped when the RC is frozen in the dark either by fast-freeze or slow-freeze procedure. The second Cu²⁺ environment, termed Cu_B, is structurally invariant to different freezing conditions and shows resolved hyperfine coupling to three nitrogen atoms. Cu²⁺ is most likely binding at the same location on the RC, but in different coordination environments which may reflect two distinct conformational states of the isolated Blc. viridis RC protein.     

Levelcrossing experiments in the first excited1 P 1 states of the alkaline earths

The hyperfine structure of the lowest¹P₁ state of²⁵Mg,⁴³Ca,⁸⁷Sr,¹³⁵Ba and¹³⁷Ba have been measured by the level-crossing and anticrossing technique. The magnetic dipole and electric quadrupole coupling constants determined by these measurements are²⁵Mg(3s3p¹P₁):A=? 7.7(5) MHz; 16 MHz>B>0 MHz,⁴³Ca(4s4p¹P₁):A=? 15.3(4) MHz; ¦B¦<12 MHz,⁸⁷Sr (5s5p¹P₁:A=? 3.4(4) MHz;B=39(4) MHz,¹³⁵Ba(6s6p¹P₁):A=? 97.5(1.0) MHz;B=31(9)MHz,¹³⁷Ba(6s6p¹P₁):A=?109.2(1.2) MHz;B=51(12)MHz. The results have been compared with the predictions of the Breit-Wills theory of the two-electron hyperfine structure using the experimental data on the³P states. Large discrepancies have been observed which are due to different radial wave functions of thes andp electron in the triplet and singlet system. This effect has been taken into account by fitting the data with the aid of two additional parameters. That this procedure is justified is shown by an analysis of the fine structure splitting, the life times, and the isotopic shifts in thesp configurations of group II elements.     

Structure of 0+ states of 28Si and particle-hole conjugation

Full sd-shell calculations for the 0⁺ states of ²⁸Si have been performed in the SU(3) basis so that the intrinsic deformation of the shell model states can be deduced by inspection. The shell model Hamiltonian is decomposed in a symmetric part H_S and an antisymmetric part H_A with respect to particle-hole conjugation. It is shown that the splitting of prolate and oblate states is due to the spin-orbit part of H_A. The different prediction for ²⁸Si obtained with Kuo and with Preedom-Wildenthal matrix elements can be attributed to the difference in a single parameter: the strength of the spin-orbit part of H_A.     

Influence of atmospheric humidity on the symmetry and phase transitions of layered potassium oxyfluorides K2NbOF5 · H2O

Crystals of K₂NbOF₅ · H₂O have been grown, polarization optical investigations have been performed, and the birefringence and rotation angle of the optical indicatrix have been measured in the temperature range 100–400 K. It has been found that, depending on the degree of atmospheric humidity, the layered K₂NbOF₅ · H₂O crystal at room temperature can be in three states, namely, A, B, and C, which differ in symmetry and properties of the crystal. The K₂NbOF₅ · H₂O crystal in the A state exists at a relative humidity RH = 90–100% and undergoes a first-order improper ferroelastic phase transition P $\bar 1$ ? C2/m, which is accompanied by strong anomalies of the optical characteristics, twinning, and shear strain x ₆ at temperatures T ₂ ^↓ = 308 K and T ₂ ^↑ = 313 K. The most stable state of the K₂NbOF₅ sdH₂O crystal is the B state (RH = 20–90%), which retains the monoclinic symmetry C2/m in the temperature range 100–370 K. In a dry atmosphere (RH = 0–20%) or at T ₁ ≈ 370 K, the crystal becomes anhydrous (K₂NbOF₅) with the symmetry P4/nmm (the C state). The difference between the crystals in the states A and B is explained by the presence or absence of water molecules in interlayer spaces.     

Ion-pair states of I<Subscript>2</Subscript>, Br<Subscript>2</Subscript>, IBr,and ICl

The experimentally determined energies and rotational constants of the vibrational levels v = 0–20 of the Ion-Pair states Ω = 0⁺, Ω = 1 of the I₂, Br₂, IBr, and ICl molecules are modeled. The model used includes three diabatic states, which correlate to X⁺(3P, 1D) + Y^～(1S₀). These states are coupled by the spin-orbit interaction, which is assumed to be independent of the internuclear distance. For IBr and ICl, as well as for the ungerade states of I₂ and Br₂, satisfactory results are obtained. The model is less applicable to the gerade states of I₂ and Br₂, which is possibly results from the retainment of the asymptotic J _A J _B coupling of the angular momenta at equilibrium internuclear distances.     

Spectroscopic properties of SbH

Relativistic configuration interaction calculations which include spin-orbit interaction are carried out for nine low-lying ω-ω states and four λ-s states. Spectroscopic properties of six bound ω-ω states are reported. These calculations not only enable assignment of the experimentally observed X₁, X₂, A₁, A₂, and B states but also predict the properties of other electronic states (0⁺(II), 0⁺(IV), 2, 2(II), 1(II), 0⁻) which are yet to be observed. The dissociation energy of SbH is predicted to be 2.7 ± 0.2 eV.     

MRCI study on spectroscopic and molecular properties of four low-lying electronic states of the BO radical

The potential energy curves (PECs) of four low-lying electronic states of the BO radical, including two ²Σ⁺ and two ²Π states, have been studied using the full valence complete active space self-consistent field (CASSCF) method followed by the highly accurate valence internally contracted multireference configuration interaction (MRCI) approach in combination with the cc-pV5Z basis set for internuclear separations from 0.05 to 2.0 nm. The effect on the PECs by the relativistic correction has been taken into account. With these PECs, the spectroscopic parameters (T_e, D₀, D_e, R_e, ω_e, ω_ex_e, α_e and B_e) of two main isotopologues (¹¹B¹⁶O and ¹⁰B¹⁶O) have been determined. These parameters have been compared in detail with those of previous investigations reported in the literature, and excellent agreement has been found between the available data and the present results. By solving the radial Schrödinger equation of nuclear motion, 60 vibrational states for the ¹¹B¹⁶O(X²Σ⁺), 60 for the ¹⁰B¹⁶O(X²Σ⁺), 66 for the ¹¹B¹⁶O(A²Π) and 64 for the ¹⁰B¹⁶O(A²Π) are predicted for the non-rotating molecule. For each vibrational state of the ¹¹B¹⁶O(X²Σ⁺), ¹⁰B¹⁶O(X²Σ⁺), ¹¹B¹⁶O(A²Π) and ¹⁰B¹⁶O(A²Π), the vibrational level G(υ), inertial rotation constant B_υ and centrifugal distortion constant D_υ have been determined. Comparison with the available data shows that the present molecular constants are reliable and accurate. The ro-vibrational levels have been calculated for the X²Σ⁺ and A²Π states of two main species for future laboratory research.     

Applications of photoelectron spectroscopy to molecular propertles: XVIII. The vertlcal ionization potentials of diphosphene as calculated by perturbation corrections to koopmans' theorem

The vertlcal ionization potentials (VIP's) of dimethyl diphosphene have been computed using perturbation corrections to Koopmans' theorem. These corrections allow an estimate of the effects of polarization and correlation, and show for this molecule an important contribution of the specific correlation of the ion for the ²A_g and ²B_u states. The results predict for the first three VIP's the ordering ²A_g, ²A_u, ²B_u, in agreement with our previous assignment.     

Rotationally resolved electronic spectrum of propadienylidene

The rotationally resolved electronic spectrum of a vibrational band in the transition of the cumulene carbon chain C₃H₂ was measured in the 625 nm region in a supersonic discharge using cw cavity ring down spectroscopy. The rotational structure was analysed using a conventional Hamiltonian for an asymmetric top molecule, and the constants A′, B′, and C′ in the upper state were determined. The observed band is assigned to a combination of a₁ and b₂ vibrations with the frequency around 2000 cm⁻¹. The geometries in the ¹A₁, ¹A₂, ¹B₁ states and the intersection point between the latter two were obtained using ab initio calculations. The effective structure in the measured vibrational level of the ¹A₂ state was inferred from the determined constants.     

The infrared spectrum of OH-compensated defect sites in C-doped MgO and CaO single crystals

The IR spectra of OH-compensated point defects in MgO (and CaO) single crystals of various purity grades were reinvestigated. Three distinct groups of IR bands appear in the O-H stretching region: A, B and C around 3550 cm^?1 (3650 cm^?1), 3300 cm^?1 (3450 cm^?1) and 3700cm^?1 (3750cm^?1). They are assigned as follows: band A to the fully compensated, band B to the half compensated and band C to the overcompensated cation vacancies, [O?V”_catH?]^×, [O?V”_cat], and [O?O?V”_catH?$\text{]}\text{?}$, respectively.Upon cooling to 80 K the band A shows a complex behavior partly due to the formation of Ha molecules by charge transfer and concommittant O^? formation: [? (H₂)”_cat?]^×. The O^? represent defect electrons or positive holes in the O^2? matrix.Bands A and B show a characteristic multiplet splitting which is caused by local lattice strains coming from carbon atoms on near-by interstitial position. The intensity ratios between the multiplet components remain constant regardless of temperature pretreatments up to 1470 K, but strong variations of the integral intensities are observed. These are caused by the highly mobile C atoms entering and leaving reversibly the cation vacancy sites as a function of temperature and of the quenching speed. When the C atoms push the H₂ molecules onto interstitial sites, an H-H stretching signal appears around 4150cm^?1.     

Minimal-disturbance measurement as a specification in von Neumann's quantal theory of measurement

In von Neumann's theory an incomplete observableA is measured by measuring any complete observableB whose functionA is. This procedure is narrowed down in this paper by the additional requirement of preservation of the sharp value of any observable compatible withA. The requirement is shown to be equivalent to the unique change of state:ρ → (trρP _n)^?1 P _nρP_n (P _n is the eigenprojector ofA corresponding to the obtained eigenvaluea _n, ρ is the statistical operator of the initial state, and by assumption trρP _n > 0). This characterises the minimal-disturbance measurement. A necessary and sufficient condition is derived for the selection of the above observableB so that its measurement implies the minimal-disturbance measurement ofA. For arbitraryρ andA, there exists aB satisfying the condition. Hence, this constitutes a reasonable specification within von Neumann's theory, reducing the latter to the physically preferable minimal-disturbance measurement theory.     

Molecular and atomic ions of the elements of the sub-groupsA of the periodic system

The production of positive and negative ions of all elements of the sub-groupsA and some of the sub-groupsB has been investigated as an extension of previous work on Penning sources. Molecular ions of the typeX _n ^± ,n>1 and ions of hydride moleculesX _nH _m ^± ,n,m>1 have been found. The maximum numberm _max of the H atoms bound in the cluster is determined by the position of the element in the periodic system. The yield of the atomic and molecular beams has been measured as a function of the electric source parameters and the different gases maintaining the discharge to establish the production mechanism. The data on ion beam intensities and the state of clustering of molecules are listed in tables.