Calculation of the electronic structure and spectra for bacteriochlorophyll analogs

Geometric structures and excited electronic states for free bases of bacteriochlorin (H₂BC) and tetraazabacteriochlorin (H₂TABC) as well as for their magnesium complexes (MgBC and MgTABC), analogs of bacteriopheophytin a (H₂BPhea) and bacteriochlorophyll a (MgBPhea), have been calculated by a DFT method and by an INDO/Sm method (the INDO/S method with parameterization modified by the authors), respectively. The factors responsible for the observed bathochromic shift of the long-wavelength Q _x (0–0) band of MgBPhea relative to H₂BPhea, \updelta E_Qx @ - 300  \textc\textm ^{- 1} {{\updelta }}{E_{{Q_x}}} \cong - 300\;{\text{c}}{{\text{m}}^{ - 1}} , have been clarified. Contributions of one- and two-electron interactions to the resulting shift of the Q _x (0–0) band have been analyzed in detail for the H₂BC/MgBC, H₂TABC/MgTABC, and porphine (H₂P)/Mg porphine (MgP) pairs. It is shown that the bathochromic shift under consideration for the tetrahydro derivatives is caused by a decrease of the orbital energy gap ε₁–ε₋₁ between the lowest unoccupied and highest occupied molecular orbitals. The variation of δ(ε₁–ε₋₁) is large and amounts to –1660 and –920 cm^–1 for the H₂BC/MgBC and H₂TABC/MgTABC pairs, respectively. The two-electron contributions, both into the energy of electronic configurations and due to the superposition of the configurations, produce a compensating hypsochromic effect such that the shifts \updelta E_Qx {{\updelta }}{E_{{Q_x}}} are –260 and –150 cm^–1 for the H₂BC/MgBC and H₂TABC/MgTABC pairs, respectively. It is also shown that the calculated electronic spectra for the considered molecules agree quantitatively with the experimental absorption spectra.     

Dependence of the Electronic Spectra of the Chlorin Molecule on the Degree of Alternation of the Macrocycle Bond Lengths

The geometric structure of the chlorin molecule (H₂Ch) has been calculated by the restricted and unrestricted Hartree-Fock (RHF and UHF) methods with an AM1 Hamiltonian. Transformations of this molecule into excited electronic states have been calculated by the CNDO/S method. The RHF method without symmetry restrictions gives a plane structure for the chlorin macrocycle with an alternation of the lengths of the bonds along the 18-member azacyclopolyene and a C_1h symmetry for the molecule as a whole. The level of the first excited state Q₁ of this structure is substantially shifted (δ ≅ +4000 cm⁻¹) relative to the Q_x level of porphin (H₂P) toward shorter waves, which is in contradiction with the experimental data, according to which this shift is long-wave and is equal to δ = −400 to −550 cm⁻¹. The optimization of the geometry of H₂Ch by the UHF method has shown that it has a structure with an 18-member azacyclopolyene with bonds of equal lengths and a D_2h symmetry. For this geometry of H₂Ch the calculated shift of the Q_x level, equal to δ = −70 cm⁻¹, is bathochromic and the position of the Q_y level is practically exactly coincident with the experimental one. For the geometry calculated by the RHF method with restrictions on the D_2h symmetry of the 18-member azacyclopolyene δ = +180 cm⁻¹, and for the geometry calculated with restrictions on the highest C_2v symmetry of the H₂Ch molecule δ = +620 cm⁻¹. The latter result shows that the “natural” requirement for the C_2v symmetry of the H₂Ch macrocycle, which is frequently used in various calculations, is inadequate to achieve a quantitative agreement between the calculation and experimental data and, in this case, the lengths of the bonds along the 18-member azacyclopolyene are not equal. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 72, No. 3, pp. 339–347, May–June, 2005.     

Laser-based measurements of line strength, self- and pressure-broadening coefficients of the H35Cl R(3) absorption line in the first overtone region for pressures up to 1 MPa

A high-resolution spectrometer based on a vertical-cavity surface-emitting laser (VCSEL) was developed and used to determine the line strength S(T ₀)=12.53(11)×10⁻²¹ cm⁻¹/(molec cm⁻²) and the self-broadening coefficient g⁰_HCl=0.021787(61)\gamma^{0}_{\mathrm{HCl}}=0.021787(61)  cm⁻¹/atm of the R(3) absorption line in the first rovibrational overtone (2←0) band of H³⁵Cl. Furthermore, the first laser-based high-pressure study on the pressure broadening of HCl by He, N₂ and O₂(g⁰_N2=0.07292(5)\mathrm{O}_{2}(\gamma^{0}_{\mathrm{N}_{2}}=0.07292(5)  cm⁻¹/atm, g⁰_He=0.02113(1)\gamma^{0}_{\mathrm{He}}=0.02113(1)  cm⁻¹/atm, g⁰_O2=0.03978(6)\gamma^{0}_{\mathrm{O}_{2}}=0.03978(6)  cm⁻¹/atm) is presented covering pressures of up to 1 MPa. The results are compared to previously available low-pressure data.     

Neutron diffraction studies of the negative thermal expansion in a layered indium selenide crystal

The neutron diffraction patterns have been analyzed for a layered single crystal and a powder of the γ-polytype of indium selenide in the temperature range 10–300 K. In the temperature range 10–50 K, the excitation of bending vibrations due to the charge density waves changes the phonon spectrum and gives rise to a negative thermal expansion in the plane of layers, i.e., α_‖c = −2.2 × 10⁻⁶ K⁻¹, which is characteristic of two-dimensional structures. The average (over the range T = 50–300 K) coefficients of thermal expansion along the principal crystallographic directions have been calculated: $ \bar \alpha _{ \bot c} $ \bar \alpha _{ \bot c} = 10.48 × 10⁻⁶ K⁻¹ and $ \bar \alpha _{\parallel c} $ \bar \alpha _{\parallel c} = 12.97 × 10⁻⁶ K⁻¹, which agree with the X-ray diffraction data previously obtained by the authors at T = 290 K.     

Reflectivity and dynamical conductivity ofn-type HgCr2Se4

Summary Reflectivity measurements have been done on dopedn-type HgCr₂Se₄ (n≈(10¹⁵÷10¹⁹) cm⁻³), at various temperatures ((4÷300) K) in the infra-red range . The spectra show the structure of a plasma edge and reststrahlbands. Data have been analysed by a Kramers-Kronig procedure. The deduced dynamical conductivity shows an anomaly near the plasma frequency ω_p. The transmitivity measurements show a strong temperature dependence of the conduction band. Paper presented at the ?V International Conference on Ternary and Multinary Compounds?, held in Cagliari, September 14–16, 1982.     

An ab initio molecular dynamics study of ionic conductivity in hexagonal lithium lanthanum titanate oxide La0.5Li0.5TiO3

To date, the fastest lithium ion-conducting solid electrolytes known are the perovskite-type ABO₃ oxide, with A = Li, La and B = Ti, lithium lanthanum titanate (LLTO) Li_3x La_{( 2 \mathord}

Transmission spectra of epitaxial layers of Pb1 ? xEuxTe (0 ≤ x ≤ 0.37) solid solutions in the frequency range 7–4000 cm?1

The spectra of epitaxial Pb_{1 − x} Eu _x Te (0 ≤ x ≤ 0.37) solid solution layers grown on BaF₂ and Si substrates have been investigated over a wide frequency range 7–4000 cm⁻¹ at temperatures of 5–300 K. Apart from the phonon and impurity absorption lines, the absorption in a local mode in PbEuTe layers of substrates and buffer layers has been observed in the frequency range 110–114 cm⁻¹. As the temperature decreases from 300 to 5 K, the transverse phonon mode softens from 33.0 to 19.5 cm⁻¹.     

Self-assembly of boehmite nanopetals to form 3D high surface area nanoarchitectures

A flower-like boehmite nanostructure was prepared through a template-free chemical route by the self-assembly process of nanosize petals 800–1000 nm long, 200–250 nm wide, 20–50 nm thick and having an average crystallite size of about 2.21 nm. X-ray diffraction analysis (XRD), transmission electron microscopy (TEM), scanning electron microscopy (SEM), DTA/TGA analyses and Brunauer–Emmet–Teller (BET-N₂) analyses were used in order to characterize the product obtained. XRD results exhibited that the obtained nanostructures composed of pure orthorhombic AlOOH phase. The effects of Cl⁻ ions and TEA on the growth of boehmite three-dimensional nanoarchitectures in the presence of NO₃^-\mathrm{NO}_{3}^{-} ions were investigated. BET analyses of as-prepared material demonstrate that this nanostructure material has a high specific surface area, as high as 123 m² g⁻¹.     

Spectroscopy study of air plasma induced by IR CO2 laser pulses

A spectroscopic study of ambient air plasma, initially at room temperature and pressures ranging from 32 to 101 kPa, produced by high-power transverse excitation atmospheric (TEA) CO₂ laser (λ=9.621 and 10.591 μm; τ _FWHM≈64 ns; power densities ranging from 0.29 to 6.31 GW cm⁻²) has been carried out in an attempt to clarify the processes involved in laser-induced breakdown (LIB) air plasma. The strong emission observed in the plasma region is mainly due to electronic relaxation of excited N, O and ionic fragments N⁺. The medium-weak emission is due to excited species O⁺, N²⁺, O²⁺, C, C⁺, C²⁺, H, Ar and molecular band systems of N ₂⁺(_{2}^{+}( B ²\varSigma _u⁺^{2}\varSigma _{\mathrm{u}}^{+} –X ²\varSigma _g⁺)^{2}\varSigma _{\mathrm{g}}^{+}) , N₂(C³ Π _u–B³ Π _g), N ₂⁺(_{2}^{+}( D² Π _g–A² Π _u) and OH(A² Σ ⁺–X² Π). Excitation temperatures of 23400±700 K and 26600±1400 K were estimated by means of N⁺ and O⁺ ionic lines, respectively. Electron number densities of the order of (0.5–2.4)×10¹⁷ cm⁻³ and (0.6–7.5)×10¹⁷ cm⁻³ were deduced from the Stark broadening of several ionic N⁺ and O⁺ lines, respectively. Estimates of vibrational and rotational temperatures of N ₂⁺_{2}^{+} electronically excited species are reported. The characteristics of the spectral emission intensities from different species have been investigated as functions of the air pressure and laser irradiance. Optical breakdown threshold intensities in air at 10.591 μm have been measured.     

Infrared spectra of BeSO4.4H2O and its deuterated analogue in 4000–1200 cm−1 region

IR spectra of BeSO₄.4H₂O and its deuterated analogue at ∼300 K and ∼110 K are reported in the region 4000–1200 cm⁻¹ using thin film and nujol mull techniques. The observed bands have been assigned as the internal modes of the water and the overtones and combinations of various modes using the recently revised assignments of SO₄ ²⁻ and Be(aq)₄ fundamentals in the region 1200–250 cm⁻¹ (Srivastavaet al 1976). The splitting of the internal modes of water has been discussed in the light of the effects of deuteration and cooling and it is shown that all the water molecules in a unit cell are asymmetric but crystallographically equivalent.     

Electrical transport properties of CuWO4

The temperature dependence of the electrical conductivity, thermoelectric power and dielectric constant of the antiferromagnetic CuWO₄ have been studied in the temperature range 300–1000 K. The conductivity results can be summarised by the equations σ_I=6.31 × 10⁻³ exp (−0.29 eV/kT) ohm⁻¹ cm⁻¹ in the temperature range 300–600 K and σ_II=3.16 × 10⁵ exp (−1.48 eV/kT) ohm⁻¹ cm⁻¹ between 600 K and 1000 K. The thermoelectric power can be expressed byθ=[− 1.25 (10³/T) + 3.9] mV/K. Initially dielectric constant increases slowly but for high temperatures its increase is fast.     

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)     

Strain-induced photoreflectance spectra in the vicinity of the E 0 transition in GaAs/Si and InP/Si heterostructures

A study is reported of the structure of photoreflectance (PR) spectra in the vicinity of the E ₀ transition from thin (d=1–5 μm) n-GaAs and n-InP films (n=10¹⁶–10¹⁷ cm⁻³) grown epitaxially on Si(001) substrates. A quantitative analysis of the spectra involving multi-component fitting shows that the electronic optical transition from the {3/2;±1/2} subband provides a dominant contribution to the intermediate-field electromodulation component in both systems. The splitting observed in the GaAS/Si PR spectra near the main peak are accounted for not by the strain-induced valence-band splitting but rather by a spectral superposition of the intermediate-field component due to the {3/2;±1/2} subband with a low-energy excitonic component. The analytically established transition energy E ₀ ^3/2;±1/2 is used to calculate biaxial strains in epitaxial films. Fiz. Tverd. Tela (St. Petersburg) 41, 725–731 (April 1999)     

Solid Substrate-Room Temperature Phosphorescence Method for the Determination of Trace Mn(II) Based on Oxidizing Reaction of Hydrogen Peroxide Using α,α′-Bipyridine as Sensitizer

A new solid substrate-room temperature phosphorescence (SS-RTP) method for the determination of trace manganese (II) has been established. It bases on the fact that fullerol (R) emits strong and stable room temperature phosphorescence (RTP) on filter paper substrate. H₂O₂ can oxidize R to cause the SS-RTP quenching. But manganese (II) can obstruct H₂O₂ to oxidize R, and enhance the RTP of R. α,α′-Bipyridine (Bipy) can sensitize the RTP. After adding Bipy, the ΔI _p enhances 7 times than that without Bipy. Under the optimum conditions, the linear dynamic range of this method is 0.016–1.12 pg spot⁻¹ with a detection limit (L.D.) of 4.6 fg spot⁻¹ ( is the absolute mass of Mn²⁺), and the regression equation of working curve is ΔI _p=25.20 + 63.55 (pg spot⁻¹), n=6, r=0.9983. For 0.016 and 1.12 pg spot⁻¹ Mn²⁺, RSDS are 4.3 and 4.8%, respectively (n=7). This method has been applied to the determination of trace manganese (II) in actual sample with high sensitivity and good selection. And the reaction mechanism of SS-RTP is discussed.     

Model for primary electron transfer and coupling of electronic states at reaction centers of purple bacteria

A detailed derivation is presented for relations making it possible to describe the effect of temperature on the halfwidth of the P960 and P870 absorption bands and also on the electron transfer (ET) rate at reaction centers (RCs) of the purple bacteria Rps. viridis and Rb. sphaeroides. Primary electron transfer is considered as a resonant nonradiative transition between P* and P⁺B _L ⁻ states (where P is a special pair, B_L is an additional bacteriochlorophyll in the L branch of the reaction center). It has been shown that the vibrational h_α mode with frequency 130–150 cm⁻¹ controls primary electron transfer. It has been found that the matrix element of the electronic transition between the states P* and P⁺B _L ⁻ is equal to 12.7 ± 0.9 and 12.0 ± 1.2 cm⁻¹ for Rps. viridis and Rb. sphaeroides respectively. The mechanism is discussed for electron transport from P* and B_L and then to bacteriopheophytin H_L. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 3, pp. 294–303, May–June, 2006.     

Spectroscopic studies of optical materials in the far infrared: The case of crystal quartz

Spectroscopic studies using far infrared reflectivity and transmissivity measurements between 10 and 600 cm⁻¹, were performed on plane parallel quartz crystal plates, in the temperature range 10–300 K. The temperature dependence of the optical mode parameters is reporeted for both polarizations parallel and perpendicular to the c-axis. The extraordinary optical constants of quartz are determined at 10 and 300 K, from the A₂ transmissivity channeled spectrum, between 10 and 300 cm⁻¹.     

Alternating current surface photovoltage in thermally oxidized chromium-contaminated n-type silicon wafers

We investigated a variation of frequency-dependent alternating current (AC) surface photovoltages (SPVs) in thermally oxidized, chromium-contaminated, n-type silicon (Si) wafers. As previously reported, immediately after rinsing in Cr-contaminated solution, a Cr(OH)₃–Si contact causes a Schottky-barrier-type AC SPV on n-type Si. Upon oxidation at 373 K for 10 min, the Schottky barrier collapses and, with further oxidation, a metal-induced negative oxide charge, due to atomic bridging of (CrOSi)⁻ and/or CrO₂^-\mathrm{CrO}_{2}^{-} networks, definitely grows over time in SiO₂. For samples oxidized at temperatures between 823 and 1023 K for 30 min, the observed AC SPV gives evidence that the metal-induced negative oxide charge causes a strongly inverted state of the Si surface. At oxidation temperatures higher than 1023 K and /or for an oxidation time longer than 60 min, the level height of the AC SPV is reduced, implying that the strongly inverted state changes into a less depleted state, whilst, finally, the AC SPV disappears. In this case, the collapse of the (CrOSi)⁻ and/or CrO₂^-\mathrm{CrO}_{2}^{-} networks is anticipated, with a possible change into Cr₂O₃. The existence of the (CrOSi)⁻ and/or CrO₂^-\mathrm{CrO}_{2}^{-} networks has also been confirmed in p-type Si wafers.     

Enhanced direct <Emphasis Type="Italic">CP</Emphasis> violation and branching ratios in bottom hadron decays

In the framework of factorization we study direct CP violation in the decays of bottom hadrons containing a strange quark or a charm quark, H _b →f ρ ⁰(ω)→f π ⁺ π ⁻ (H _b is the bottom hadron and f is the product hadron) including the effect of ρ–ω mixing. We find that the CP violating asymmetry can be enhanced greatly via the ρ–ω mixing mechanism when the invariant mass of the π ⁺ π ⁻ pair is in the vicinity of the ω resonance. For the processes associated with b→d transitions, e.g. , , B _c ⁻→D ⁻ π ⁺ π ⁻, B _c ⁻→D ^*− π ⁺ π ⁻, Ξ _b ⁰→Λ π ⁺ π ⁻, and Ω _b ⁻→Ξ ⁻ π ⁺ π ⁻, the maximum CP violating asymmetries can reach about −84%, while for the processes associated with b→s transitions, e.g. , , B _c ⁻→D _s ⁻ π ⁺ π ⁻, B _c ⁻→D _s ^*− π ⁺ π ⁻, Ξ _b ⁻→Ξ ⁻ π ⁺ π ⁻, and Ω _b ⁻→Ω ⁻ π ⁺ π ⁻, the CP violating asymmetries can be enhanced to about 95%. Furthermore, taking ρ–ω mixing into account we calculate the b-hadron decay branching ratios. We also discuss the possibility to observe the predicted CP violating asymmetries at the LHC.