Substituent effect on electron affinity,gas‐phase basicity,and structure of monosubstituted propargyl radicals and their anions: a theoretical study

The substituent effect of electron‐withdrawing groups on electron affinity and gas‐phase basicity has been investigated for substituted propargyl radicals and their corresponding anions. It is shown that when a hydrogen of the α‐CH₂ group or acetylenic CH in the propargyl system is substituted by an electron‐withdrawing substituent, electron affinity increases, whereas gas‐phase basicity decreases. The calculated electron affinities are 0.95 eV (CH?C? CH₂?), 1.15 eV (CH?C? CHF?), 1.38 eV (CH?C? CHCl?), 1.48 eV (CH?C? CHBr?) for the isomers with terminal CH and 1.66 eV (CF?C? CH₂?), 1.70 eV (CCl?C? CH₂?), 1.86 eV (CBr?C? CH₂?) for the isomers with terminal CX at B3LYP level. The calculated gas‐phase basicities for their anions are 378.4 kcal/mol (CH?C? CH₂:^?), 371.6 kcal/mol (CH?C? CHF:^?), 365.1 kcal/mol (CH?C? CHCl:^?), 363.5 kcal/mol (CH?C? CHBr:^?) for the isomers with terminal CH and 362.6 kcal/mol (CF?C? CH₂:^?), 360.4 kcal/mol (CCl?C? CH₂:^?), 356.3 kcal/mol (CBr?C? CH₂:^?) for the isomers with terminal CX at B3LYP level. It is concluded that the larger the magnitude of electron‐withdrawing, the greater is the electron affinity of radical and the smaller is the gas‐phase basicity of its anion. This tendency of the electron affinities and gas‐phase bacisities is greater in isomers with the terminal CX than isomers with the terminal CH. Copyright © 2009 John Wiley & Sons, Ltd.     

Kinetics,mechanism and thermodynamics of reactions of CH3NHNH2 with OOH

Reactions between CH₃NHNH₂ and OOH radical were studied using computational methods. The activation energies (E_a) and Gibbs free energies of activation (ΔG^#) were calculated at the MP2 and B3LYP levels of theory. The calculated activation energies of the hydrogen abstraction reactions were less than 100 kJ/mol and those for the substitution reactions were about 150–250 kJ/mol. The calculated activation energies for the intra-molecular hydrogen transfer reactions in CH₃NHNH, CH₂NNH₂ and CH₃NN molecules were 210–250 kJ/mol. Catalytic effect of the water molecule on the intra-molecular hydrogen transfer reactions was studied. It was found that the water molecule decreases the activation energies by about 70–100 kJ/mol. Rate constants of the reactions were calculated using transition state theory in the temperature range of 298–2000 K. Consecutive hydrogen abstraction reactions from CH₃NHNH₂ led to the formation of CH₂NN, which was a very stable molecule.     

Electric and electrochemical properties of solid LiH2PO4

Electrical and electrochemical properties of solid LiH₂PO₄ conductor were investigated in the temperature range from room temperature to 373 K. It was found that high conductivity throughout the temperature range, with activation energy 17.23 kJ/mol, originates from the movement of hydrogen ions (protons). The movement of protons in the correlation with phosphate groups rotation was considered. The slopes of Tafel lines and exchange current densities both for cathodic hydrogen and anodic oxygen evolution were determined (by means of usual electrochemical kinetic methods) at various temperatures. The energy of activation at the equilibrium potentials both for the cathodic and the anodic processes have been assessed to be 17.23 kJ/mol (0.18 eV) and 2.9 kJ/mol (0.03 eV), respectively.     

Pressure broadening of the ground vibrational state J = 31→J = 32 transition of CH3F by coincidence laser spectroscopy

We have studied self-broadening and foreign gas broadening of the ground state J = 31→J = 32 transition of CH₃F using a coincidence with the 184.3 μm emission from an optically pumped CH₂F₂ laser. Experiments have been carried out with polar and non-polar species as well as the noble gases.This transition is in the region where the classical rotation period is of the same order as the duration of a collision. The measurements indicate an anomalously low value of 7.0 MHz/Torr for the self-broadening coefficient of CH₃F and an unusually large value for the CH₃OH broadening coefficient. The latter is believed to be due to the presence of a low energy OH torsional model in CH₃OH.     

Internal hydrogen bond,torsional motion,and molecular properties of 2-methoxyethylamine by microwave spectroscopy: Methyl barrier to internal rotation for 2-methoxyethanol

The microwave spectra of four substituted isotopic species of 2-methoxyethylamine (NH₂, NHD, NDH, ND₂) have been assigned. The molecule is found to exist in a gauche form with an intramolecular hydrogen bond of the NH?O type. The four possible sets of the amino hydrogen r_s corrdinates give different H?H distances, probably because the -NH₂ group is involved in large amplitude vibrations and because of changes in the heavy atom positions arising from the deuteration of the hydrogen bond. For the most abundant species many vibrational states have been analyzed and assigned to the two possible CO torsions in the molecule. A value V₃ = 3150 ± 50 cal/mol was found for the methyl torsional barrier and V₁ = 9 ± 3 kcal/mol for the other CO torsional barrier. A third set of observed vibrational satellites is probably assignable to the CC torsion. The determination of the dipole moment and of the quadrupole coupling constants gave values which were not in good agreement with those predicted from nonhydrogen bonded molecules. In addition a value V₃ = 3100 ± 100 cal/mol was calculated for the CH₃ torsional barrier in the related 2-methoxyethanol, using previous experimental data (Canad. J. Chem.50, 1149–1156 (1972)).     

Internal rotation and inversion doubling in the microwave spectrum of CH3NHCl

The microwave “a” and “c” type spectra of four isotopic species of CH₃NHCl in the ground state and of CH₃NHCl³⁵ and CH₃NDCl³⁵ in the first excited torsional state have been analyzed. From the A-E torsional splittings of the excited state the torsional barrier height has been determined to be V₃ = 3710 ± 46 cal/mole. The “c” type transitions show an inversion doubling of 4.60 ± 0.10 MHz in the ground state and of 5.25 ± 0.10 MHz in the first excited torsional state. Such doublings are independent on the rotational quantum numbers within the experimental errors. The height of the inversion barrier has been roughly evaluated by using the Dennison-Uhlenbeck potential.     

Methyl group tunnelling and torsion in 2,4-hexadiyne

The tunnelling splitting of the ground torsional level of solid 2,4-hexadiyne and transitions to excited torsional states have been measured at low temperatures using neutron inelastic scattering. At 4 K the tunnelling splitting is 1·060 μeV (0·0086 cm^-1). It decreases as the temperature is raised, to 0·834 μeV (0·0067 cm^-1) at 35 K, and to less than 0·6 μeV at 50 K. A V-2←V=0 transition in the torsional vibration has been observed at 222 cm^-1 which shifts to 160 cm^-1 in the fully deuterated compound.

The values of the torsional frequencies, tunnelling frequency, and the change of tunnelling splitting with temperature have been fitted exactly to a potential energy for rotation of a methyl group given by

with a barrier to rotation of 432 cm^-1.

Changes in the tunnelling transitions as the temperature increases are compared with existing theories of the mechanism.     

Electron spectroscopy with excited atoms and photons.: X. Halogen-substituted methanes and methyl amines

Electron binding energy spectra have been measured for CH₃Cl, CH₃Br, CH₃I, CFCl₃, CF₂Cl₂, CF₃Cl, CF₄, CH₃NH₂, (CH₃)₂ NH and (CH₃)₃N. Measurements have been made using 584 Å (21.22 eV) photons as well as with 2³S(19.82 eV) and 2¹S(20.62 eV) metastable helium atoms. Relative spectral intensities are compared for photoionization and Penning ionization.     

Thermostimulated creep in amorphous polyolefins. I

The thermostimulated creep of two amorphous polyolefins having the repeating unit ─(CH₂)_mC(CH₃)2─, where m = 2 and 3, was investigated from 77° to 350°. Two relaxation processes are distinguished: a secondary relaxation is observed at 138 and 113°, respectively, for m = 2 and m = 3; a primary relaxation is found around the glass transition. These relaxations have been resolved in their elementary components. From the data acquired, the mechanical losses have been calculated and compared with data from an inverted torsional pendulum. The activation energy found for the secondary relaxation—0.26 eV at 138° K for the amorphous polyolefin with m = 2 and 0.19 eV at 113° K for the polyolefin with m = 3—confirms that this relaxation mode is associated with restricted backbone motion.     

Conformational and structural studies of n‐propylamine from temperature dependent Raman and far infrared spectra of xenon solutions and ab initio calculations

The Raman and infrared spectra (4000 to 50 cm^–1) of the gas, liquid or solution, and solid have been recorded of n‐propylamine, CH₃CH₂CH₂NH₂. Variable temperature (−60 to −100 °C) studies of the Raman (1175 to 625 cm^–1) and far infrared (600 to 10 cm^–1) spectra dissolved in liquid xenon were carried out. From these data, the five possible conformers were identified and their relative stabilities obtained with enthalpy difference relative to trans–trans (Tt) for trans–gauche (Tg) of 79 ± 9 cm^–1 (0.9 ± 0.1 kJ/mol); for Gg of 91 ± 26 cm^–1 (1.08 ± 0.3 kJ/mol); for Gg′ of 135 ± 21 cm^–1 (1.61 ± 0.2 kJ/mol); for Gt of 143 ± 11 cm^–1 (1.71 ± 0.1 kJ/mol). The percentage of the five conformers is estimated to be 18% for the Tt, 24 ± 1% for Tg, 23 ± 3% for Gg, 18 ± 1% for Gg′ and 18 ± 1% for Gt at ambient temperature. The conformational stabilities have been predicted from ab initio calculations utilizing several different basis sets up to aug‐cc‐pVTZ from both second‐order Møller–Plesset (MP2, full) and density functional theory calculations by the Becke, three‐parameter, Lee–Yang–Parr method. Vibrational assignments were provided for the observed bands for all five conformers, which are supported by MP2(full)/6‐31G(d) ab initio calculations to predict harmonic force constants, wavenumbers, infrared intensities, Raman activities and depolarization ratios for both conformers. Estimated r₀ structural parameters were obtained from adjusted MP2(full)/6‐311+G(d,p) calculations. The results are discussed and compared with the corresponding properties of some related molecules. Copyright © 2012 John Wiley & Sons, Ltd.     

紫外光诱导光电子发射负离子源的阈值光电子成像仪设计 (cited: 2)

设计了一套紧凑的光电子成像装置,它包括解离式光电子贴附负离子源、垂直安装的高分辨阈值光电子速度成像装置和线性飞行时间质谱仪．紫外光辐射金属表面诱导低能光电子发射,再通过低能电子贴附超声分子束产生高强度和冷的负离子源．结合这种负离子源和飞行时间质谱-光电子成像仪装置,仪器的质量分辨能达到200左右,能量分辨优于3%(即对1 eV动能的电子,分辨达到30 meV)．此外,使用该实验装置获得了CH₃S^-和S₂^-在611.46 nm下的低能阈值光电子成像结果．同时得到了CH₃S和S₂的更精确的电子亲和势分别为1.8626±0.0020和1.6744±0.0035 eV．初步的结果证明了该装置对研究阈值光电子成像精确测量光电子亲和势非常有效     

Internal rotation in the spectrum of acetaldehyde

The geometrical structure of acetaldehyde from the microwave spectrum and torsional transitions from the far infrared spectrum have been fitted with a semirigid model in order to obtain the torsional parameters V″₃ = 415.0 and V″₆ = 22.3 cm^?1 and the torsional energy levels of the isotopic species CH₃CHO, CH₃CDO, CD₃CHO, and CD₃CDO. These have been used in fitting torsional sequences in the 182-nm system of the electronic spectra of these species to obtain the excited state parameters V′₃ = 880 and V′₆ = 77 cm^?1. Both the ground and excited state parameters are in good agreement with ab initio predictions.     

等离子体氧轰击硅生成缺陷的研究

本文对等离子体氧轰击硅产生的缺陷进行了研究。发现等离子体氧轰击在硅中引入两个缺陷E₁(E_c—0.46eV)及E₂(E_c—0.04eV)。测量了缺陷的光电离截面谱,分析表明,缺陷E₂的电子声子相互作用很强,其Frank-Condon移动达0.76eV,缺陷E₁的电子声子相互作用较小,其Frank-Condon移动为0.04eV。由实验结果得到与缺陷E₁、E₂相耦合的声子模分别为hω_p⁽¹⁾=28meV,hω_p⁽²⁾=20meV。 关键词：     

Core photoelectron spectroscopy of some acetylenic molecules

Carbon 1s binding energies have been measured for CH₃CCH, CH₃CCCH₃, CF₃CCH and CF₃CCCF₃ and compared to a verified value for acetylene. Assignments are based on the application of a CNDO potential model with relaxation corrections which is quite successful in predicting binding energy shifts and upon qualitative considerations. Substitution of CF₃ groups shifts the acetylenic C 1s binding energy from 291.2 (HCCH) to 292.2 in CF₃CCH and 292.7 eV in CF₃CCCF₃. The unequal substitutional shifts are probably due to a saturation of substituent effect expected in competitive situations. With reservations arising from uncertainties in assignment due to lack of resolution, it appears that acetylenic C 1s binding energies decrease [to 290.7 (av.) in CH₃CCH and to 290.1 eV in CH₃CCCH₃] upon replacement of H by CH₃ groups. Although the decrease in acetylenic binding energies agrees with the chemical notion that CH₃ groups are electron donating with respect to unsaturated portions of the molecule, theoretical calculations available in the literature indicate that actual electron withdrawal or donation does not occur in these differently substituted molecules. The shifts of apparent binding energy correlate reasonably well with a ground state potential model which accounts for the effect of the charge on the adjacent atoms as well as on the photoionized atom. Even better correlation is obtained if the atomic potentials are corrected for electronic redistribution (relaxation) effects which occur during the photoionization process, and it is suggested that relaxation effects make a significant contribution to shifts of apparent binding energies. Surprisingly ground state potential and relaxation corrected potential calculations with the CNDO method suggest a large difference in C 1s binding energies of the two acetylenic carbon atoms in CH₃CCH which is not verified experimentally nor mirrored by calculations on CF₃CCH. The CH₃ binding energies are 291.8 eV in CH₃CCH and 291.3 eV in CH₃CCCH₃, both higher than values assigned to CH₄ or C₂H₆.     

Hyperfine structure of <Emphasis Type="Italic">S</Emphasis>- and <Emphasis Type="Italic">P</Emphasis>-wave states in muonic-helium ion

Corrections of order α ⁵ and α ⁶ to the hyperfine structure of S- and P-wave energy levels of the muonic-helium ion are calculated. Electron-vacuum-polarization effects, corrections for the nuclear structure, and recoil effects are taken into account. The numerical values obtained for respective hyperfine splitting, −1334.73 meV (1S), −166.64 meV (2S), −58 712.90 μeV (2P _1/2), and −24 290.69 μeV (2P _3/2), can be viewed as a reliable estimate for a comparison with experimental data, and the hyperfine-structure interval of Δ₁₂ = 8ΔE ^hfs(2S) − ΔE ^hfs(1S) = 1.59 meV can be used to test QED predictions.     

硅中金受主能级在单轴应力下瞬态电容的研究

用恒定温度下瞬态电容法研究了硅中金受主能级在沿〈100〉,〈110〉,〈111〉晶向单轴应力作用下的能级移动。考虑到硅的导带在单轴应力下的分裂,导出了单轴应力下深中心中电子发射率的公式。根据该式和发射率的实验数据以及切变畸变势常数Ξ_u,求出了金受主能级激活能随应力的改变。在实验应力范围内(0—9kbar),激活能与应力成线性关系。当应力平行于〈110〉〈111〉晶向时,激活能随应力改变的斜率分别为α_<110>=-3.2±0.6meV/kbar,α_<111>=-0.3±0.6meV/kbar;当应力平行于〈100〉晶向,若取Ξ_u=9.2eV,α_<100>=-5.8±0.8meV/kbar,若取Ξ_u=11.4eV,α_<100>=-5.3±0.8meV/kbar,α表现出强烈的各向异性。进一步确定了金受主能级相对于零压力下导带底的绝对移动的压力系数。若取Ξ_u=9.2eV,这些系数分别为S_<100>=-1.3±0.8meV/kbar,S_<110>=0.7±0.6meV/kbar,S_<111>=-0.7±0.6meV/kbar。如取Ξ=11.4eV,则S_<100>=-3.5±0.8meV/kbar,S_<110>=0.0±0.6meV/kbar,S_<111>=-1.0±0.6meV/kbar。同一组的三个绝对移动值之间的偏离都超过了实验误差这一事实,说明了金中心具有立方对称性,同时中性金与带负电的金的基态都是非简并的可能性很小。 关键词：     

Millimeter-wave spectrum and internal rotation of 1-silylpropyne,CH3CCSiH3

Rotational transitions of CH₃CCSiH₃ have been observed in the millimeter-wave region using a computer-controlled source-frequency modulation spectrometer with a 1.8-m-long free space absorption cell. The observed spectrum clearly showed the effect of internal rotation with a small potential barrier. It has been analyzed by calculating the torsion-rotation energies on the basis of torsional wave functions obtained by diagonalizing the torsional part of the Hamiltonian. The least-squares analysis has yielded the rotational constant B = 2068.2817(4) MHz and a few centrifugal distortion constants. The barrier height to internal rotation has been determined to be 3.77(70) cm^?1 from the contour map of the standard deviation. Also, the A rotational constant of the silyl group around the symmetry axis has been estimated by fixing the A constant of the methyl group to the value of CH₃CCH.     

Rotational spectrum, structure and internal rotation in CH3CCl3

The rotational spectra of the v₆ = 1 and v₆ = 2 torsional states of CH₃C³⁵Cl₃ have been measured in the millimeterwave range and accurate spectroscopic constants have been determined. The equilibrium structure, the torsional frequency and the barrier to internal rotation have been calculated ab initio. These results are shown to be compatible with the absence of splittings in the rotational spectra.     

Optical absorption of zinc selenide doped with cobalt (Zn1−xCoxSe) under hydrostatic pressure

Abstract

The optical absorption of the diluted magnetic semiconductor Zn_1?xCO_xSe (x = 0.02) has been measured at room temperature under hydrostatic pressure up to 14GPa in a membrane diamond-anvil cell. We found two absorption features: (i) an absorption structure in the energy range 1.6?1.8eV, with a negligible pressure shift (i.e., 0.45 ± 0.05 meV/GPa) which we have identified as the Co²⁺(3d⁷) internal transition ⁴A₂(F)→+⁴T₁(P) and (ii) an onset in the energy range 2?2.7eV which redshifts with pressure (?8.1±0.6meV/GPa). We have attributed such absorption edge to charge transfer between the ZnSe valence band and the Co²⁺(3d⁷) levels.     

Torsional refilling transitions in tea-pumped CH3OH fir lasers with associated high-resolution fir spectra

It is proposed that a number of the high-frequency far-infrared (FIR) laser lines observed when CH₃OH is optically pumped by high-power CO₂ TEA lasers can be identified as refilling torsional transitions within the vibrational ground state. Assignments are presented for 8 such TEA-pump/FIR-laser refilling systems. To provide support for the assigned laser frequencies, high-resolution Fourier transform FIR spectra of CH₃OH have been obtained and partially analyzed in the torsional transition region.