Analytical form of the interaction energy of radicals at short and long distances

The interaction potential between two planar methyl radicals is investigated based on the available ab initio calculations. Two components contribute to this potential: a bonding potential, V _B, an angle-dependent square of the overlap integral for unoccupied p _s orbitals, and a nonbonding potential, V _NB, a total of the long-range dispersive and short-range repulsive interactions. The analytical form of the potential, valid at longer distances, can be used for evaluation of the matrix elements of functions describing rotational states.     

Quantum chemical investigation of the reaction of O(3 P 2) with certain hydrocarbon radicals

The reaction of ground-state atomic oxygen [O(³ P ₂)] with methyl, ethyl, n-propyl and isopropyl radicals has been studied using the density functional method and the complete basis set model. The energies of the reactants, products, reaction intermediates and various transition states as well as the reaction enthalpies have been computed. The possible product channels and the reaction pathways are identified in each case. In the case of methyl radical the minimum energy reaction pathway leads to the products CO + H₂ + H. In the case of ethyl radical the most facile pathway leads to the products, methanal + CH₃ radical. For propyl radical (n- and iso-), the minimum energy reaction pathways would lead to the channel containing ethanal + methyl radical.     

Recombination of tert-butyl radicals: the role of weak van der Waals interactions

A mechanism for the recombination of tert-butyl radicals is postulated to involve the loosely bonded intermediates tert-C₄H₉⋯tert-C₄H₉. Three processes contribute to the overall recombination rate constant: tert-C₄H₉+ tert-C₄H ⇆ tert-C₄H₉⋯tert-C₄H₉ characterized by the equilibrium constant K ₁ and tert-C₄H₉⋯tert-C₄H₉ → C₈H₁₈* characterized by the rate constant k ₂, k _rec,∞(T) ≈ K ₁ k ₂. This recombination rate constant exhibits a negative temperature dependence and is proportional to T ^−3/2. The agreement with experiment is very good. Received: 2 October 2000 / Accepted: 2 May 2002 / Published online: 7 August 2002     

DFT and direct ab-initio MD study on hyperfine coupling constants of methyl radicals adsorbed on model surface of silica gel

Methyl radicals interacting with silica gel surfaces have been investigated by means of DFT and direct ab-initio molecular dynamics (MD) methods using cluster models. Four typical binding sites of CH₃ on the cluster models were found in the geometry optimization from several initial geometries of CH₃ around the silica gel clusters. These were two silanol Si–OH sites and two siloxane Si–O–Si sites. In both sites, magnitude of hyperfine coupling constants of the methyl radical (a_H) was smaller than that of free CH₃ (a_H = 23.04 G). Temperature effects on a_H of the methyl radical were investigated by means of the direct ab-initio MD method. The hyperfine coupling constant of CH₃ interacting with the SiOH group decreased with increasing temperature. The methyl radical interacting with alkali metal supported silica gel was also investigated for comparison. The electronic states of methyl radicals on silica gel were discussed on the basis of theoretical results.     

Energy levels of two interacting particles in an anharmonic potential

Energy levels of two interacting mass points in an anharmonic model potential (Morse type) have been studied. Analytic expression for the energy levels has been worked out. The model potential is shown to support bound states under certain conditions. The number of such states has been found to depend on the parameters of the potential. The potential is expected to be more realistic, particularly in presence of environments for diatomic molecules and artificial atoms. © 2004 Wiley Periodicals, Inc. Int J Quantum Chem, 2005     

Effects of chain transfer and recombination/disproportionation of inhibitor radicals on inhibited oxidation of lipids

The kinetics of inhibited oxidation of lipids was studied by computer simulation to evaluate the contributions of the recombination/disproportionation of inhibitor radicals and chain transfer to retardation effects. The influence of inhibitor regeneration on the induction periods and inhibited oxidation rate was demonstrated. Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 10, pp. 1915–1920, October, 1999.     

Studies on State-to-State Energy Transfer of Electronically Excited Atoms and Molecules

Rotationally inelastic collisions of NH₂( òA₁), ∑(0,9,0), 3₀₃, 1₀₁ have been studied by measuring the dispersed fluorescence spectra at molecular beam conditions. The results show that the angular momentum transfer rule is much more successful than is that predicted by energy gap law for fitting the rotational energy transfer rate. For ΔN < 2 the transfer rates are getting slow down. Downward transfer rates are faster than those of upward transfer. With same angular momentum transferred, the transfer rates for Δk_a = 0 process are larger than those for Δk_a≠0. It is also found that rotation transfer process is a very efficient way for decaying of the initially pumped levels. About 60% of the initially pumped 3₀₃ is colliding into other rotational levels. Energy transfer reactions of metastable rare gas atoms (R_g*) with N₂, NH₃, CS₂ were investigated by measuring the emission spectra. The preferential population of n(A″) of NH(c¹II) was found in He(2³S) + NH₃ reaction, the experimental data shows II(A″)/II(A′) = 1.2 at J′ < 13. A high vibrational excitation and low rotational excitation of N₂(C³n) were observed in Ne(³P₀₂) + N₂ reaction comparing with Ar(³P_0.2) + N₂ reaction. The detailed vibrational populations of CS₂⁺ (Ã, B?) achieved by He(2³S)/Ne(³P_0.2) + CS₂ reaction are different from those obtained by PES. The vibrational distributions of CH(A²Δ) obtained by He(2³S) + CHC1₃ (CH₃NO₂) reactions were discussed based on statistical theory, special attention was paid to reveal the role played by tie angular momentum restriction in this process. The result on energy transfer between N₂(a¹ Π) and CO(X¹ ∑) was firstly presented by VUV emission spectra at single collision condition. The mechanisms of energy transfer related to some of the reactions mentioned above were also discussed in the text.     

UF6分子的模型伸缩振动能级的计算

利用一个四参数非线性模型,对处于电子基态下的XY6型分子的X-Y键的伸缩振动进行了描述,并将其应用于计算UF6分子中U-F键的伸缩振动能级.计算中引入的模型Hamilton算符所包含的描述U-F键非谐振动的参数λ和描述U-F键之间的偶极-偶极相互作用参数ε1, ε2由实验值得出,波函数|ψn〉按形式为|n,α〉=|n1〉|n2〉|n3〉|n4〉|n5〉|n6〉的基函数集展开,从而把复杂的Hamilton方程转化为简单的矩阵代数方程.结果显示,该非线性模型能够较好地描述UF6分子的振动( 计算误差在1.0 cm-1之内 ),同时合理地预测了一些至今还未观测到的能级值.     

Prediction and assignment of site occupation and energy levels for Pb ions in crystal hosts

The environmental factor h_e of the host was calculated quantitatively in Pb²⁺-doped 23 compounds based on the dielectric theory of chemical bond for complex crystals. The relationship between the A band energy E_A of Pb²⁺ and the environmental factor h_e was intensively studied. The results indicate that E_A of Pb²⁺ decreases linearly with increasing of h_e. A linear model was proposed which allows us to correctly predict and assign the site occupations and the position of A band for Pb²⁺-doped compounds if the crystal structure and the refraction index were known. Applied to SrGa₂O₄:Pb²⁺, CaAl₂B₂O₇:Pb²⁺ and SrAl₂B₂O₇:Pb²⁺, the theoretical predictions are in very good agreement with the experimental data. In SrGa₂O₄:Pb²⁺, the excitation spectrum of Pb²⁺ from two different cation sites was identified: the higher energy band of A (265 nm) from the site of Sr2, and the lower ones (280 nm) from the site of Sr1.     

Persilylated phosphoranyl radicals: the first persistent noncyclic phosphoranyl radicals

Persistent noncyclic phosphoranyl radicals have been prepared and observed by electron paramagnetic resonance (EPR) for the first time. They were obtained by UV-photolysis of a solution containing a bis(trialkylsilyl) peroxide (R = Me, Et) and a tris(trialkylsilyl) phosphite (R = Me, Et, iPr). EPR parameters (a(P) approximately 100 mT) are typical of phosphoranyl radicals exhibiting a trigonal-bipyramidal structure, with the odd electron in an equatorial site. Analysis of the pseudo-first-order decay shows that these phosphoranyl radicals decay by S(H)2 homolytic substitution on the bis(trialkylsilyl) peroxide and by loss of a trialkylsilyloxyl radical (alpha-scission reaction). Both the S(H)2 and alpha-scission reactions depend on the steric bulk of the alkyl groups, that is, the bulkier the alkyl group, the slower the S(H)2 and alpha-scission reactions.     

Photogeneration of the free radicals and singlet oxygen by chrysophanol from rheum

Chrysophanol (3-methyl-1,8-dihydroxyanthraqui-none) belongs to a family of anthraquinone pigmentsthat naturally exist in many kinds of plants, such asrheum, a Chinese herbal medicine growing abundantlyin China. Besides their biological activities, thesepigments are also well known as photosensitizers[1,2].Photosensitizers are able to photochemically producehighly reactive species, such as O2, O2 , ?OH, and 1 ??induce a series of damage to biologic…     

水杨酸甲酯清除羟基自由基活性的研究

利用脉冲辐解技术研究了水杨酸甲酯清除羟基自由基反应的瞬态吸收谱,测定了水杨酸甲酯与羟基自由基反应的表观速率常数。辅以常规检测方法,测定了水杨酸甲酯对羟基自由基的清除率。结果表明,水杨酸甲酯能快速有效清除羟基自由基。探讨了水杨酸甲酯清除羟基自由基的反应机制。     

Nuclear Energy Reserves and Long-Term Energy Requirements

In this article the world's potential energy reserves are summarized on the basis of available estimates, and the future energy consumption is estimated with the aid of a working hypothesis relating to the growth of the world's population (P) and the energy consumption per capita (γ). According to this estimate, the energy requirements in 30 years will be about seven times and in 80 years about fifty times as high as they are today, and all the concentrated energy sources will be exhausted in about 120 to 160 years. – The energy requirements in the steady state (P_γ = const.) could be of the order of 10¹³ MWh per year and could be met out of magmatic rocks (U,Th) and sea water (U,D). High priority should be given to research and development work on the construction, reliability, and safety of breeder and fusion reactors, the chemical treatment and final disposal of radioactive waste, the extraction of uranium, thorium, and deuterium from the “primitive” raw materials, the relevant problems relating to protection of the environment, and the worldwide control of the excess birthrate.     

The use of stabilized radicals with monomers and lauroyl peroxide

Three nitroxides (viz TEMPO and its 4-hydroxy- and 4-oxo-derivatives) have been used at 60 °C as inhibitors of the homopolymerizations of methyl methacrylate and acrylonitrile with lauroyl peroxide as initiator and toluene, tetrahydrofuran or dimethylformamide as diluent; diphenylpicrylhydrazyl has also been used as an inhibitor. The dependencies of the inhibition period upon the initial value of [inhibitor]/[initiator] and on the nature of the reaction medium resemble those found when using benzoyl peroxide as initiator in similar systems. The polymers of methyl methacrylate formed after inhibition have quite low average molecular weights and, when using the nitroxides, the polydispersities are comparatively small. There is discussion of the significance of the findings.     

Direct kinetic study of the reaction of OH radicals with methyl-ethyl-ketone

The low-pressure discharge flow technique with resonance fluorescence monitoring of OH has been applied to study the kinetics of the overall reaction:

ESR study of the radicals obtained from adducts of dialkyl itaconates with bromotrichloromethane

Three kinds of bromides were prepared from the reaction of dialkyl itaconates with bromotrichloromethane as precursors of analogous radicals for the propagating radicals of some dialkyl itaconates, i.e., the methyl, deuterated methyl, and adamantyl ester derivatives. The radicals were generated by photoirradiation of a toluene solution of the bromides in the presence of hexabutylditin at −60 to 60°C, and ESR spectra were recorded. Hyperfine splitting and the temperature dependence of the linewidth were determined. The β-deuterated radicals were also characterized to determine a coupling to β-hydrogens. © 1999 John Wiley & Sons, Inc. J Polym Sci A: Polym Chem 37: 1969–1978, 1999     

势阱中粒子能级与波函数微扰计算的代数递推公式

利用超位力定理(HVT)和Hellmann-Feynman 定理(HFT),导出了由有精确解的势阱的能级值用微扰法直接计算一维势阱的各级近似能级的普遍代数公式,并导出了由能级近似值计算定态波函数近似表达式的代数公式.给出了代数公式具体应用的几个典型一维势阱实例.此法可推广到二维势阱与三维势阱的情形.     

CO(α3П)与CN(X 2Σ +)的能量转移反应

Energy-transfer reaction from metastable CO(a~3П) molecule to CN radical has been studied in a room-temperature flow reactor. The CN (B-X, △v=0, ±1, ±2) violet emission bands were obtained. The △v=0 sequence of CN(B) were analyzed by computer simulation. The vibrational temperature is 3400 K. By using the reference reaction CO(a)+NO, the formation rate constant of CN(B) has been measured, k_(CN)(B)=1.1×10~(-11) cm~3·molecule~(-1)·s~(-1).     

Absorption Spectrum of Neutral Krypton in the Near Infrared Region

High-resolution absorption spectra of atomic krypton in the range of 11870-12700 cm^?1 were recorded by employing concentration modulation absorption spectroscopy technique with a tunable single-mode cw Ti:Sapphire laser. The krypton atoms were excited to the absorbing energy states by discharge-burning in a mixture of helium and krypton. A total of 120 lines of neutral krypton were observed, among them 33 lines had already been classified in previous studies, 45 lines were newly classi ed with the known energy levels, and 42 lines cannot be classi ed. These unclassified lines indicate that up to now unknown energy levels of Kr must exist. Further, an analysis of the unclassi ed lines to get possible new energy levels with a classi cation program is reported.     

ESR study of formation of allylic radicals in simultaneous photochemical generation of phosphoryl and carbon-centered radicals in the presence of C60 fullerene

Allylic radicals resulting upon simultaneous photochemical generation of phosphoryl [^.P(O)(OPrⁱ)₂] and carbon-centered [^.C(O)OMe,^.CH₃,^.CCl₃] radicals in saturated toluene solutions of C₆₀ have been studied by the ESR method. The donor-acceptor properties of carbon-centered radicals determine the positions of phosphoryl groups in the allylic system.Translated fromIzvestiya Akademii Nauk. Seriya Khimicheskaya, No. 12, pp. 2422–2424, December, 1995.This work was performed under terms of the Russian Interdisciplinary Scientific and Technical Program Fullerenes and Atomic Clusters and was financially supported by the Russian Foundation for Basic Research (Project Nos. 93-03-18725 and 93-03-4101) and the International Scientific and Technical Center (Grant No. 079 (B)).