Electron affinities,molecular structures,and thermochemistry of the fluorine,chlorine and bromine substituted methyl radicals

Four independent density functional theory (DFT) methods have been employed to study the structures and electron affinities of the methyl and F-, CI- and Br-substituted methyl radicals and their anions. The methods used have been carefully calibrated against a comprehensive tabulation of experimental electron affinities (Chemical Reviews, 2002, 102, 231). The first dissociation energies together with the vibrational frequencies of these species are also reported. The basis sets used in this work are of double-ζ plus polarization quality with additional s- and p-type diffuse functions, labelled as DZP++. Previously observed trends in the prediction of bond lengths by the DFT methods are also demonstrated for the F-, Cl- and Br-substituted methyl radicals and their anions. Generally, the Hartree-Fock/DFT hybrid methods predict shorter and more reliable bond lengths than the pure DFT methods. Neutral-anion energy differences reported in this work are the adiabatic electron affinity (EA_ad), the vertical electron affinity (EA_vert), and the vertical detachment energy (VDE). Compared with the available experimental electron affinities, the BHLYP method predicts much lower values, while the other methods predict values (EA_ad, EA_vert, VDE) close to each other and almost within the experimental range. For those systems without reliable experimental measurements, our best adiabatic EAs predicted by BLYP are 0.78 (CHF₂), 1.23 (CHFCl), 1.44 (CHFBr), 1.61 (CHClBr), 2.24 (CF₂Cl), 2.42 (CF₂Br), 2.56 (CFBr₂), 2.36 (CCl₂Br), 2.46 (CClBr₂), and 2.44 eV (CFClBr). The most striking feature of these predictions is that they display an inverse relationship between halogen electronegativity and EA. The DZP++B3LYP method determines the vibrational frequencies in best agreement with available experimental results for this series, with an average relative error of ～2%. The value of using a variety of DFT methods is observed in that BHLYP does best for geometries, BLYP for electron affinities, and B3LYP for vibrational frequencies. These theoretical results serve to resolve several disagreements between competing experiments. Several other experiments appear to have drawn incorrect conclusions. For example, CHCl₂ is significantly pyramidal, unlike the experimental inferences, and clearly the experimental CCl₂—Cl dissociation energy is too large.     

Electron-impact ionization and excitation of helium to the n=1-4 ionic states

We present high-precision (e,2e) measurements and calculations for the e-He four-body Coulomb breakup problem. Cross-section ratios for ionization and excitation of the first three excited states of He+ relative to the ground state have been measured for incident energies between 112 and 319 eV. Comparing the data with predictions from a state-of-the-art hybrid distorted-wave+convergent R matrix with pseudostates (close coupling) approach shows that treating the projectile-target interaction at least to second order is crucial to obtain reasonable agreement between theory and experiment. Nevertheless, our benchmark studies reveal significant theoretical problems for the symmetric energy-sharing cases, thus indicating the need for further improvement.     

Electron affinities of cyano-substituted ethylenes

Electron affinities of ethylene and six cyano-substituted ethylenes (cyanoethylene, 1, 1-dicyanoethylene, cis-1, 2-dicyanoethylene, trans-1, 2-dicyanothylene, tricyanoethylene, and tetracyanoethylene) were determined using six different density functional or hybrid Hartree-Fock/density functional methods. Equilibrium geometries and harmonic vibrational frequencies for each species were determined with each density functional method. Experimental electron affinities exist for three of the six systems studied (cyanoethylene, trans-1, 2-dicyanoethylene, and tetracyanoethylene); for the three systems, the absolute average EA errors for the different methods are 0.10eV (BLYP), 0.19ev (BHLYP), 0.22eV (B3LYP), 0.20eV (BP86), 0.78eV (B3P86), and 0.81eV (LSDA). The electron affinities of gem-dicyanoethylene, cis-discyanoethylene, and tricyanoethylene are not known from experiment but are predicted here to be 1.23eV (gem-dicyanoethylene), 1.32eV (cis-dicyanoethylene), and 2.41eV (tricyanoethylene). Contrary to earlier suggestions, tetracyanoethylene is predicted to be planar, rather than twisted. Density functional theory predicts that the ²B_1u state of the ethylene anion lies lower than the ²B_2g state, which is reported by experimentalists as the (transient) ground state, and lower than the ²A_g state. Coupled-cluster results indicate that the ²A_g state is lower than either the ²B_2g or ²B_1u states. The energetic stabilization of cyano substitution on ethylene results from the π and π? conjugation of multiple cyano groups. The HOMO-LUMO gap in ethylene decreases with increasing cyano substitution, from 7.2eV in C₂H₄ to 3.8eV in C₂(CN)₄, explaining the extreme difference between the electron affinities of ethylene (negative) and tetracyanoethylene (～T3.0eV).     

MgmBn(m=1,2;n=1-4)团簇结构与性质的密度泛函理论研究

用密度泛函理论(DFT)的杂化密度泛函B3LYP方法在6-31G*基组水平上对MgmBn(m=1,2;n=1-4)团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构.并对最稳定结构的振动特性、电离势、成键特性、极化率和超极化率等性质进行了理论研究.结果表明,团簇的最稳定结构大多是平面结构,团簇的稳定结构中通常是几个呈负电性的B原子形成一个负电中心,而其他B原子和Mg原子通常处在端位,且显正电性;团簇中通常是B-B键和B-Mg键共存,极少出现Mg-Mg键,计算得到的B-B键键长在0.153-0.182nm之间,B-Mg键键长在0.221-0.231nm之间.     

NiMgn(n=1-12)团簇的第一性原理研究

采用基于密度泛函理论(DFT)中的广义梯度近似(GGA),在考虑自旋多重度的情况下,对NiMgn(n=1-12)团簇进行了构型优化,频率分析和电子性质计算.结果表明:n=1,2时,体系的基态为自旋三重态,n≥3时.为单重态;Ni原子掺杂使主团簇结构发生了明显变化.n≤8时,三角双锥,四角双锥结构主导着NiMgn基态团簇的生长行为;n在9-12之间时,主团簇Mgn 1(n=1-12)的基于三棱柱构型的基态演化行为发生了一定程度的改变;n≥6时,Ni原子陷入了主团簇内部;掺杂使体系的平均结介能增大,能隙减小;n=4,6,10是团簇的幻数;不同尺寸团簇的s,p,d轨道杂化中,Ni原子3d,4p成分所起作用不同;NiMg6基态结构具有很高的对称性(Oh),很好的稳定性和化学活性,能隙仪为0.25 eV.     

Electron affinities of some elements

Photodetachment cross sections of several atomic negative ions have been measured in order to supply a fairly complete set of experimental values for the electron affinity EA of the elements of the short periods.     

Measurement of the collisional transition rate between the hydrogen levels n = 3 and n = 4

The ratio of the collisional transition rate C₄₃ and the total loss rate V₄ of the level n = 4 has been measured by means of dye-laser fluorescence in a rf hydrogen plasma. In a further experiment using a nitrogen-laser-pumped dye-laser (with pulses short compared to the life time of the n = 4 level), the total loss rate V₄ of this level has been determined by observing the exponential intensity decay of the H_β line. From the results of these two experiments, the excitation rate C₄₃ is obtained. Agreement with theoretical values is found.     

Two-dimensional charge order in layered 2-1-4 perovskite oxides

Monte Carlo simulations are performed on the three-dimensional (3D) Ising model with the 2-1-4 layered perovskite structure as a minimal model for checkerboard charge ordering phenomena in layered perovskite oxides. Because of the interlayer frustration, only 2D long-range order emerges with a finite correlation length along the c axis. Critical exponents of the transition change continuously as a function of the interlayer coupling constant. The interlayer long-range Coulomb interaction decays exponentially and is negligible even between the second-neighbor layers. Instead, monoclinic distortion of a tetragonal unit cell lifts the macroscopic degeneracy to induce a 3D charge ordering. The dimensionality of the charge order in La0.5Sr1.5MnO4 is discussed from this viewpoint.     

(Ca3N2)n(n=1-4)团簇结构与性质的密度泛函理论研究

用密度泛函理论(DFT)的杂化密度泛函B3LYP方法在6-31G*基组水平上对(Ca3N2)n(n=1-4)团簇各种可能的构型进行几何结构优化,预测了各团簇的最稳定结构.并对最稳定结构的振动特性、成键特性、电荷特性和稳定性等进行了理论分析.结果表明,(Ca3N2)n(n=1-4)团簇最稳定构型中N原子为3-5配位,Ca-N键长为0.231-0.251 mm,Ca-Ca键长为0.295-0.358 nm;N原子的自然电荷在-1.553 e--2.241 e之间,Ca原子的自然电荷在1.035e-1.445e之间,Ca和N原子间相互作用呈现较强的离子性,Ca3N2和(Ca3N2)3团簇有相对较高的动力学稳定性.     

Effect of Sb substitution on the superconductivity of Bi2(Ca,Sr) n+1Cu n O4n+2 (n=1, 2 and 3) systems

Effect of incorporation of Sb in place of Bi in the bismuth cuprate superconductors has been examined. The nominal compositions studied are MCa_1·5Sr_1·5Cu₂O_8+δ and MCa₂Sr₂Cu₃O_10+δ, whereM=Bi_2−x Sb _x or Bi_1·5−x Sb _x Pb_0·5. Different preparative routes such as the ceramic method, the matrix route as well as the melt route were employed to prepare the materials. No indication of either Sb entering the lattice or enhancement ofT _c is noted from resistivity, magnetic susceptibility and microwave absorption measurements. Communication No. 162 from Materials Research Centre.     

TinMg(n=1-10)掺杂团簇的密度泛函研究

采用密度泛函(DFT)中的B3LYP方法,选择sto-3g基组,优化并得到了TinMg(n=1-10)小团簇的基态平衡结构,计算出了掺杂团簇的基态结构的平均键长、对称性、原子化能、能级分布、能级间隙、束缚能、总能的二阶差分.结果表明,随着团簇原了数的增加.镁原子更容易趋于团簇表面位置,镁-钛平均键长大于钛-钛平均键长,以对称性结构为最稳定的基态结构,且呈多个五角双锥结构.其中Ti5Mg和Ti8Mg的结构更为稳定.     

Hydrogen atom transfer in indole clusters: formation dynamics of , n = 1-6, fragments

The H atom transfer reaction in electronically excited indole(NH ₃ ) _n clusters is studied in pump-probe experiments with femtosecond laser pulses. By applying different probe photon energies we are able to detect the dissociation products (NH ₃ ) _{n - 1} NH ₄ for n = 1-6. Furthermore we show that the analysis of the corresponding ion signals is not distorted by contributions from larger cluster ions due to evaporation of NH ₃ molecules. The formation times of the products are ca. 140ps for n = 2-4 and about 80ps for n = 5, 6. Received 30 April 2002 / Received in final form 29 May 2002 Published online 13 September 2002     

(MgO)(-)(n) (n = 1-5) clusters: multipole-bound anions and photodetachment spectroscopy

Photoelectron spectra of (MgO)(-)(n) (n = 1-5) reveal a surprising trend: The electron binding energy decreases from n = 1 to 4, and then increases from 4 to 5. Ab initio calculations suggest this pattern is related to the electrostatic interaction between the extra electron and the charge distribution of the neutral cluster. This interaction is significant in MgO (-) and (MgO)-5, for which the lowest nonvanishing multipole moment (LNM) is a dipole; it is smaller for (MgO)-2 and (MgO)-3, for which a quadrupole is the LNM; and it is the smallest for (MgO)-4, for which an octopole is the LNM. The cubic (MgO)-4 is the first octopole-bound anion yet observed experimentally and characterized theoretically.     

Ab initio structures and stabilities of helide cations: (X = B-Ne, Al-Ar and n = 1-3)

The electronic structure and molecular properties of helides of the form (where , Al-Ar and ) were studied using the CCSD(T) method in conjunction with the series of correlation-consistent basis sets. The highest level of theory employed, the CCSD(T)_-FC/cc-pVQZ model, was used to elucidate trends in bond lengths, dissociation energies and harmonic frequencies. The more highly charged species were found to have shorter bond lengths than the singly charged species. The ground states of the helide cations were often those with longer bond lengths when compared with the excited state ions. Received: 11 May 1998 / Received in final form: 2 September 1998     

Electron affinities of the radicals derived from thymine tautomers

The structures, energies, and electron affinities of the tautomers of dehydrogenated thymine radicals (T-H) have been studied theoretically. Geometry optimizations were carried out utilizing the density functional theory (DFT) methods with double-ζ quality basis sets plus polarization and diffuse functions (DZP++). These methods have been carefully calibrated for the prediction of electron affinities. Significant structural differences were found among thymine 24 dehydrogenated radicals and their corresponding anions from thymine tautomers. The electron affinities for these radicals are in the range of 0.96 and 3.88 eV, contrasting with the much smaller electron affinities associated with the closed-shell thymine tautomers. Among these investigated radicals those with removal of a hydrogen atom from the nitrogen atoms present the larger electron affinities (EAs).     

Measurements of theP 3/2-S 1/2-intervals in then=4,n=5 andn=6 states of ionized helium

TheP _3/2-S _1/2-intervals in then=4,n=5 andn=6 states of ionized helium have been measured by a radio frequency method, which permits to determine the disturbing electric fields in the interaction region and to correct their influences. The experimental results for theP _3/2-S _1/2 intervals in then=4,n=5 andn=6 states were (20,180.6±0.8) MHz, (10,332.9±1.4) MHz and (5,979.1±1.2) MHz respectively. From these intervals, the following indirect values for theS _1/2-P _1/2-Lambshifts can be deduced: (1,768.5±0.8) MHz in then=4 state, (905.0±1.4) MHz in then=5 state and (524.3±1.2) MHz in then=6 state. The results agree with the theoretical predictions. The static electric fields in the interaction region, ranging from 2 to 6 V/cm, increased with increasing electron excitation current, but were independent of the helium pressure within the range of 10 to 26 mTorr. All uncertainties are expressed as 68% confidence values.