BF自由基X1∑+和a3∏态光谱常数和分子常数研究

采用内收缩多参考组态相互作用方法和相关一致基aug-cc-pV6Z, 对BF自由基X¹∑⁺和a³∏ 态的势能曲线进行了研究. 计算是在0.095---1.33 nm的核间距内进行的. 为获得更准确的结果, 计算中还考虑了Davidson修正、相对论修正及核价相关修正对势能曲线的影响. 相对论修正采用的方法是二阶DouglasKroll哈密顿近似, 修正计算是在cc-pV5Z基组水平上进行的. 核价相关修正使用的是cc-pCV5Z基组. 利用得到的势能曲线, 拟合出了各种修正下BF自由基X¹∑⁺和a³∏ 态的光谱常数D_e, R_e, ω_e, ω_ex_e, ω_ey_e, B_e和α_e、并与实验结果进行了比较. 结果表明: 考虑Davidson修正、相对论修正和核价相关修正后得到的光谱常数最接近实验结果. 利用修正后的势能曲线, 通过求解径向振转Schrödinger方程, 找到了转动量子数J = 0时这两个电子态的全部振动态, 并计算了每一电子态前20个振动态的振动能级、惯性转动常数和离心畸变常数, 其值与已有的实验结果较为一致. 本文得到的光谱常数和分子常数达到了很高的精度, 能为进一步的光谱实验提供可靠的参考.     

Dynamics of photosensitized singlet oxygen generation and photophysical characteristics of chlorin <Emphasis Type="Italic">e</Emphasis><Subscript>6</Subscript> in photolon ointment

We have used luminescence and absorption spectroscopy to study the dynamics of photosensitized singlet oxygen generation and the photophysical characteristics of chlorin e ₆ in Photolon ointment. We have shown that dimethylsulfoxide and polyethylene glycol 400, in concentrations comparable with their content in the ointment form of the drug Photolon, do not lead to appreciable changes in the spectral characteristics of chlorin e ₆. Substantial changes in the photophysical characteristics of the photosensitizer are observed at significantly higher concentrations of the excipients in the ointment. We have shown that in buffer solution, chlorin e ₆ forms a complex with polyethylene glycol 1500. For the first time, we have detected luminescence of singlet oxygen from the surface of biological tissue treated with Photolon ointment.     

Spectral-Luminescent Studies of the “Photolon” Photosensitizer in Model Media and in Blood of Oncological Patients

Using the methods of steady-state absorption and fluorescence spectroscopy and flash-photolysis, the new photosensitizer Photolon (Stock Company Belmedpreparaty) and its basic chromophore part — the substance chlorin e ₆ — have been studied under model conditions. It has been shown that there are no considerable differences between the spectral-luminescent characteristics of Photolon and chlorin e ₆ at a concentration not exceeding 2.5·10^–5 M in ethanol, phosphate-saline buffer (pH 8.5), and isotonic solution. That is, the polyvinyl-pyrrolidone (PVP) entering into the composition of Photolon does not influence the chromophore characteristics being investigated. It has been found that an increase in the mass fraction of PVP in the buffer solution of chlorin e ₆ leads to an increase in the degree of polarization of chlorin e ₆ fluorescence and to a change in the spectral-luminescent and kinetic characteristics, pointing to the fact that the pigment is built into the hydrophobic portions of the polymer. Using the method of multiple scattering of light, it has been shown that both Photolon and chlorin e ₆ are present in the whole blood of donors and oncological patients mainly in the monomeric form; Photolon is quickly removed from the blood of patients (after 24 h, C 10^–3 mg/ml).     

Optical absorption spectrum of the silver dimer ion: temperature dependence measured by photodissociation and photon-trap spectroscopy

The optical absorption spectrum is reported for the silver dimer cation, Ag₂ ⁺, which is temperature-controlled by buffer-gas cooling in an ion trap. The measurement is performed by two methods, photodissociation and photon-trap spectroscopy. The temperature of the trapped ions is estimated from the profiles of the spectrum. The spectrum is further analyzed to evaluate the bond length, r _e , the vibrational frequency, ω _e , and the anharmonic constant, ω _e x _e , in the first excited electronic state based on the molecular parameters reported for the ground state. Absorption and dissociation cross sections are compared as well.     

Spectral-Fluorescent Properties of Supramolecular Systems Based on Chlorin e<Subscript>6</Subscript>

The spectral-fluorescent properties of various supramolecular systems based on chlorin e₆ (Ce₆) are determined to facilitate the development of new medicines for photodynamic therapy and diagnostics. The effect of various excipients, such as poly-N-vinylpyrrolidone (PVP), polyethylene glycol (PEG), bovine serum albumin (BSA), chitosan, Triton X-100 (TX-100), sodium hexametaphosphate (SHMP), and poly(dimethyldiallylammonium chloride) chloride (PDDAC), on the optical absorption and fluorescence of Ce₆ is demonstrated. In the Ce₆?PVP, Ce₆?PEG, Ce₆?BSA, Ce₆?TX-100, Ce₆?SHMP, and Ce₆?PDDAC systems, Ce₆ molecules are disaggregated and complexes thereof with excipients are formed. The quantum yield of Ce₆ fluorescence in supramolecular systems is close to that of the free-form photosensitizer, in the absence of excipients. The results suggest that supramolecular complexes of Ce₆ are promising for the development of medicines with controllable photodynamic activity.     

The vibrational numbering and improved constants of the A3Π1u state of I2

The A-X system of I₂ has been recorded in absorption, under conditions of medium resolution, over the region 8000 – 13 400 Å. Bandheads in progressions based on v″ = 6 through 18 have been measured and assigned. A new vibrational numbering for the A state is proposed, which leads to more reliable values for the important constants of the A state: T_e = 10 906 ± 3 cm^?1, D_e = 1641 ± 3 cm^?1, ω_e = 92.5 ± 0.5 cm^?1, ω_ex_e = 1.20 ± 0.08 cm^?1, ω_ey_e = ?0.062 ± 0.006 cm^?1.     

On the electronic properties of the sulfur nitride polymer (SN)x

Results of an ab initio LCAO Hartree-Fock crystal orbital calculation are reported for (SN)_x using a double-zeta type atomic basis set. In contrast with previous minimal basis calculations the width of the metallic half-filled band is only ～ 4 eV in this study. The calculated effective mass (1.7m_e), electron state density [0.14/(ev spin molecule)] and transferred charge (～0.4e from sulfur to nitrogen) are also in good agreement with experiment.     

MgH分子X2Σ+，A2Π和B2Σ+电子态的势能函数

利用QCISD(T),SAC-CI方法和cc-pVQZ,aug-cc-pVTZ,6-311++G及6-311++G(3df,2pd)基组,对MgH分子的基态X²Σ⁺,第一简并激发态A²Π和第二激发态B²Σ⁺的结构进行优化计算.通过对4个基组计算结果进行比较,得出6-311++G(3df,2pd)基组为最优基组.使用 关键词： 分子结构与势能函数 激发态 Murrell-Sorbie函数 C₆函数')" href="#">Murrell-Sorbie+C₆函数     

The influence of phonons on the optical properties and the conductivity of quasi-one-dimensional metals

The frequency dependent conductivity σ(ω) completely taking into account the interaction between electrons is studied. The shape and the temperature dependence of optical absorption near the frequency of a molecular phonon activated due to the interaction with electrons are found. For a system with attractive sign of the e-e backward scattering amplitude g₁<0 an absorption edge near the gap 2Δ in the electronic spectrum is studied. A low frequency conductivity is discussed. The properties under consideration depend essentially on the magnitudes of e-e interactions and are critical to the sign of g₁.     

The out-of-plane vibrational modes of chlorobenzene in its ground and first singlet excited states

The study of 2699 Å electronic band system of chlorobenzene has been extended to extract out all the six b₁ and three a₂ modes in both the ground state (^eA₁) and the electronically excited first singlet state (^eB₂). The procedure of the extraction of these modes on the basis of observed sequences, cross-sequences, and overtones has especially been elaborated. Strong Fermi interaction has been observed between the vibrational level ν′_6b and combination level ν′_16a + ν′_16b in ^eB₂ state. The uniqueness of the assignments of the modes has been critically discussed.     

Spectral Luminescence Properties of Potassium Aluminophosphate Glass Doped with Four-Valence Vanadium Complexes

Potassium aluminophosphate glass with the composition 30 K₂O-20 Al₂O₃-50 P₂O₅ (wt %) doped with four-valence vanadium was prepared and analyzed. Some physicochemical properties of the glass obtained and its absorption and luminescence spectra were investigated at 300 K. The existence of oxovanadium ions in the prepared glass was proved on the basis of the electronic absorption data. The bands observed in the electronic absorption spectrum were assigned to the e→b ₁ and e→a ₁ transitions. Intense luminescence of four-valence vanadium in the wavelength range 800–1100 nm was found. The average luminescence decay time amounts to 12 μs. __________ Translated from Optika i Spektroskopiya, Vol. 96, No. 6, 2004, pp. 926–928. Original Russian Text Copyright ? 2004 by Batyaev, Linnikov, Lipatova.     

Quantum interference effects in a multi-driven transition Fg = 3 ↔ Fe = 2

We calculated and studied the quantum coherence effects of a degenerate transition F_g = 3 ↔ F_e = 2 system interacting with a weak linearly polarized (with σ_± components) probe light and a strong linearly polarized (with σ_± components) coupling field. Due to the competition between the drive Rabi frequency and the Zeeman splitting, electromagnetically induced transparency (EIT) and electromagnetically induced absorption (EIA) are appeared at the different values of applied magnetic field in both cases that the Zeeman splitting of excited state Δe is smaller than the Zeeman splitting of ground state Δg (i.e., Δe < Δg) and Δe > Δg. It is shown that the resonance is broader and contrasts are higher for Δe < Δg than that for Δe > Δg at the same Rabi frequencies of probe and coupling fields.     

Thermal transport in chemically doped polyaniline materials

Simultaneous measurements of effective thermal conductivity (λ_e) and effective thermal diffusivity (χ_e) of four samples S1 (polyaniline mixed with 100% Ni), S2 (polyaniline mixed with 90% Ni and 10% Al), S3 (polyaniline mixed with 80% Ni and 20% Al) and S4 (polyaniline mixed with 70% Ni and 30% Al) of polyaniline mix with metal Ni and Al in different percentage have been made using transient plane source technique. In the temperature range from room temperature to 170 °C. Both λ_e and χ_e increase with increase in temperature. Addition of aluminium concentration at the cost of nickel in the composite increases the value of λ_e and χ_e over the entire range of temperature under investigation. It has been found that the values of λ_e and χ_e are maximum when 70% of Ni and 30% of Al are mixed in polyaniline matrix. This behaviour is also predicted by an empirical relation, which is obtained from polynomial fit of the experimental data and is explained on the basis of bond formation between metal (Ni and Al) and nitrogen of polyaniline matrix.     

Dynamics and efficiency of the photosensitized singlet oxygen formation by chlorin <Emphasis Type="Italic">e</Emphasis><Subscript>6</Subscript>: The effects of the solution pH and polyvinylpyrrolidone

The effects of the solution pH and polyvinylpyrrolidone on the dynamics and efficiency of the formation of singlet oxygen ¹O₂ in buffer media (pH 6.3–8.5) photosensitized by chlorin e ₆ are studied. It is demonstrated that the quantum yield of the ¹O₂ formation photosensitized by chlorin e ₆ decreases with decreasing solution pH due to the aggregation of photosensitizer molecules. Polyvinylpyrrolidone facilitates the disaggregation of chlorin e ₆, thus increasing its photosensitizing ability. For a complex of chlorin e ₆ with this polymer, the luminescence kinetics of singlet oxygen is inverted, which should be taken into account in the determination of the lifetime of ¹O₂ in real biological systems.     

Spectral and photochemical characteristics of the photosensitizers chlorin <Emphasis Type="Italic">e</Emphasis><Subscript>6</Subscript> and photolon in the presence of melanin

The effect of DOPA melanin on the spectral and kinetic properties of the photosensitizers chlorin e ₆ and Photolon in buffer solutions with different pH (8.5, 7.0, and 6.0) is studied. The data obtained indicate that no complex formation between molecules of DOPA melanin and either photosensitizer in the ground or excited states occurs (at least, at melanin concentrations ≤0.1 mg/ml). The presence of melanin in the samples has no effect on the spectral-luminescent or kinetic characteristics of either chlorin e ₆ or Photolon. At a small concentration of DOPA melanin (≤0.02 mg/ml), the quantum yield of generation of singlet oxygen by the photosensitizers does not change; however, the generation efficiency of singlet oxygen decreases due to the shielding action of melanin.     

Theoretical studies of chemisorbed oxygen on Ag(110)

The interaction of an oxygen atom with a 26-atom cluster model of the (110) face of Ag has been investigated with ab initio self-consistent-field and configuration-interaction theory. The SCF results for the bridge site (C_2v) predict $\text{r = 0.3}\text{A}\text{?}$ and ω_e = 327 cm^?1, in good agreement with the available experimental evidence. The calculated binding energy (D_e = 9 kcal/mole) is roughly an order of magnitude too small. The inclusion of electron correlation increases r_e and ω_e only slightly, but should have a dramatic effect on D_e. The ground state corresponds to a “surface oxide” state. The theoretical projected density-of-states curves exhibit “bonding” and “anti-bonding” O(2p) peaks, separated by ~ 6 eV, in good agreement with recent angle-resolved photoemission data.     

The 2880-Å emission spectrum of I2: Ion-pair states near 47 000 cm−1

An emission system of I₂ in Ar in the region 2830–2890 Å is examined under high resolution and found to display fine violet-degraded band structure. This system is interpreted as a charge-transfer transition originating from an ion-pair state near 47 000 cm^?1 and terminating on a weakly bound state which dissociates to two ground-state atoms. This interpretation is supported by spectral simulations employing a bound-free model. The transition is tentatively assigned as $\text{0}{}_{\mathrm{<mtext>g</mtext>}}{}^{\mathrm{?}}\text{→ 2431 0}{}_{\mathrm{<mtext>u</mtext>}}{}^{\mathrm{?}}\text{(}{}^3\text{Π}\text{)}$, according to which the excited state becomes the fourth ion-pair state near 47 000 cm^?1 to be experimentally characterized, and the lower state is the last component of the lowest ³Π state to be identified. The vibrational assignments include about 45 bands in ¹²⁷I₂ and ¹²⁹I₂, spanning v′ = 0–4 and v″ = 6–19, but with the numbering of the lower state remaining uncertain by several units. The main spectroscopic constants for the excited state are T_e = 47 070 cm^?1, ?_e = 105.7 cm^?1, ?_ex_e = 0.49 cm^?1. The spectral simulations place the lower state's potential curve 34 650 cm^?1 below the upper state at R = R′_e, with slope ?850 cm^?1/Å. For our “best” numbering of the lower state, ?_e = 20.5 cm^?1, ?_ex_e = 0.29 cm^?1, T_e = 12 190 cm^?1, and D_e = 360 cm^?1.     

Laser-induced photodynamic effects of chlorinse 6 andp 6 on an isolated neuron

Photodynamic effects of chlorins e₆ and p₆ on an isolated mechanoreceptor neuron of a fluvial crayfish are investigated. A He−Ne laser (632.8 nm, 0.3 W/cm²) was used as an excitation source. The impulsive activity of neurons was found to be extremely sensitive to the photodynamic effect of low concentrations of chlorins e₆ and p₆ (0.005–6.000 and 0.05–0.50 μM, respectively). Cell reactions consisted of several phases of acceleration and inhibition of pulsations followed by an irreversible cancellation of nervous pulse generation. The type of reaction depended on the photosensitizer form and concentration. It is supposed that the phases of acceleration of impulsive activity are connected with the photodynamic damage of the cell membrane, and the inhibition phases are connected with the photodynamic effect on intracell organells. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 2, pp. 250–255, March–April, 1999.     

Experimental Determination of Ground and Excited State Dipole Moments of N,N-Bis (2, 5-di-tert-butylphenyl)-3, 4:9, 10-perylenebis (dicarboximide) (DBPI) A Photostable Laser Dye

In the present work, the absorption, emission spectra and dipole moments(μ_g, μ_e) of N, N-bis (2, 5-di-tert-butylphenyl)-3, 4:9, 10- perylenebis (dicarboximide) (DBPI) have been studied in solvents of various polarities at room temperature. Using the methods of solvatochromism, the difference between the first excited singlet state (μ_e) and ground state (μ_g) dipole moments was estimated from Lippert – Mataga,, Bakhshiev, Kawski – Chamma – Viallet equations. The change in dipole moment (Δμ) was also calculated using the variation of the Stokes shift with microscopic solvent polarity parameter (E _T ^N ). It was observed that the value of excited singlet state dipole moment is higher (3.53 Debye) than the ground state one (1.92Debye), showing that the excited state of DBPI is more polar than the ground state.     

Ab initio calculations on the spectroscopic constants, vibrational levels and classical turning points for the 21∏u state of dimer 7Li2

The accurate dissociation energy and harmonic frequency for the highly excited 2^1Пu state of dimer ^7Li2 have been calculated using a symmetry-adapted-cluster configuration-interaction method in complete active space. The calculated results are in excellent agreement with experimental measurements. The potential energy curves at numerous basis sets for this state are obtained over a wide internuclear separation range from about 2.4a0 to 37.0a0. And the conclusion is gained that the basis set 6-311＋＋G（d,p） is a most suitable one. The calculated spectroscopic constants De, Re, ωe, ωeχe, ae and Be at 6-311＋＋G（d,p） are 0.9670 eV, 0.3125 nm, 238.6 cm^-1, 1.3705 cm^-1, 0.0039 cm^-1 and 0.4921 cm^-1, respectively. The vibrational levels are calculated by solving the radial SchrSdinger equation of nuclear motion. A total of 53 vibrational levels are found and reported for the first time. The classical turning points have been computed. Comparing with the measurements, in which only the first nine vibrational levels have been obtained so far, the present calculations are very encouraging. A careful comparison of the present results of the parameters De and We with those obtained from previous theories clearly shows that the present calculations are much closer to the measurements than previous theoretical results, thus representing an improvement on the accuracy of the ab initio calculations of the potentials for this state.