Phonon dispersion treatment for the heat capacities of vitreous and crystalline phases

Based upon the Barker and Martin treatment developed for the analysis of vitreous phases, an analysis of both polycrystalline and crystalline phases of various complexity is described. Primarily, cryogenic heat-capacity measurements and spectroscopic vibrational analysis are involved. Some history of the development of the phonon dispersion equations is incorporated. The applicability of the phonon velocity dispersion to polycrystalline and single-crystal copper are used as convenient examples to illustrate the application of the theory. They emphasize the complications occasioned by anisotropies in single crystals even in polycrystalline aggregates, where they are only partially obscured by the macroscopic isotropy of aggregates. Copper does involve the treatment of the electronic terms and demonstrates a competence of critical relevance to other types of crystalline and vitreous materials.     

Quantitative assessment of the degree of hoarseness

By using a computer simulation, the author examined the theoretically expected discrepancy of the obtained H/N ratio from the real H/N value, the effects of perturbatios of pitch, and amplitude on the H/N ratio and others. Regarding the averaged wave as an estimate of the harmonic component, resulted in harmonic energy greater than its real value. The H/N ratio method detected perturbations of pitch and amplitude as a quantity of noise energy. The effect of pitch perturbation on the H/N ratio was much greater than that of amplitude perturbation. The error range of the measurement system did not contribute significantly to the calculated H/N ratios.     

Charge-transfer properties of the hydrogen bond: Part 6. Charge-transfer theory and dipole moments of hydrogen-bonded complexes

The enhancement of the dipole moments of hydrogen-bonded complexes are discussed using Mulliken's charge-transfer theory.A linear relation is found between the ratio a/b and the ionization potential of the donor, I^V_D. This behaviour is similar to that previously found for halogen charge-transfer complexes [6].     

Overall values of conventional discrepancy indices for crystals with heavy atoms. Part II. Results for monoclinic and orthorhombic crystals when the heavy-atom part alone constitutes the model

Theoretical expressions of 〈y _N〉, 〈|y _N − σ₁ y _P ^c |〉 and 〈|y _N ² −σ ₁ ² (y _P ^c )²|〉 (wherey _N andy _P ^c are the normalized structure amplitudes of the structure and the model respectively) are derived in terms of the heavy atom contributionσ ₁ ² for monoclinic and orthorhombic crystals containing a few (i.e., 1 or 2) heavy atoms of the same kind per asymmetric unit by taking the heavy atom part alone as the model. Results are obtained for both the related and unrelated cases. The local values of 〈y _N〉 and 〈|y _N ⁿ − σ ₁ ⁿ (y _P ^c ) ⁿ |〉, (n=1, 2) calculated from these expressions can be used to calculate the overall values of the conventionalR-indicesR(F) andR(I) for the related and unrelated cases. These overall values could be used to check the correctness of heavy atoms located in the structure. Contribution No. 550     

Theoretical evaluation of the overall values of unnormalized discrepancy indices for truncated data in crystals obeying Wilson distributions

Theoretical expressions for the local values of six types of unnormalized R-indices are derived for an imperfectly related incomplete model of a crystal (centrosymmetric and non-centrosymmetric) with truncated data which is characterized by a truncation limit y _t. These indices depend on the parameters σ ₁, D and y _t. In the situations of practical interest (i.e., σ ₁ ² >0·3 and y _t<0·2) R-indices for the centro-symmetric case decrease as y _tincreases while these for the non-centro-symmetric case remain more or less constant. Contribution No. 569     

炉内成球法制备PVA涂层理论模拟研究

 根据炉内成球法制备PVA涂层原理，建立了炉内成球法在PS微球表面制备PVA涂层的数学模型，并利用数值方法进行了求解，研究了初始PS壁厚和直径、载气种类、炉内温度、PVA含量等实验条件的影响。计算结果表明，包裹PS微球的PVA水溶液复合微球在下落过程中速度迅速增加，短时间内达到最大值后又逐渐降低；复合微球的PVA水溶液涂层厚度逐渐减少，微球表观密度降低；炉内温度较低时，PVA涂层不易烘干；空气和纯Ar做炉内气氛时，微球烘干时间延长，而在He和Ar混合气体中，随着He含量增加，微球烘干时间缩短；小直径PS微球及高含量PVA溶液有利于制备厚的PVA涂层。     

直冷电冰箱制冷循环分析

分析了直冷电冰箱单路、双路、多路循环及双机、双级制冷循环,进行了系统匹配性、市场占有率、成本及其COP值比较。针对双路循环存在的频繁开停机现象,提出了完善控制方式及采用双稳态电磁阀的变温技术。变温室蒸发器与冷冻室蒸发器串联,其前串联双稳态电磁阀2,并在变温室蒸发器上并联双稳态电磁阀1,据变温室温度设定改变双稳态电磁阀通断实现两个循环支路交替制冷。冷藏室温度控制压缩机启停,变温室温度仅控制双稳态电磁阀通断,实现切换制冷剂流向目的。应用该循环方式及相关措施研制的BCD-188CH直冷电冰箱最大负荷日耗电0.38度,变温情况下耗电在0.35度以下,最低达0.31度。     

Theoretical study on the kinetics for OH reactions with CH3OH and C2H5OH

Kinetics and mechanisms for reactions of OH with methanol and ethanol have been investigated at the CCSD(T)/6-311 + G(3df, 2p)//MP2/6-311 + G(3df, 2p) level of theory. The total and individual rate constants, and product branching ratios for the reactions have been computed in the temperature range 200-3000 K with variational transition state theory by including the effects of multiple reflections above the wells of their pre-reaction complexes, quantum-mechanical tunneling and hindered internal rotations. The predicted results can be represented by the expressions k₁ = 4.65 × 10⁻²⁰ × T^2.68 exp(414/T) and k₂ = 9.11 × 10⁻²⁰ × T^2.58 exp(748/T) cm³ molecule⁻¹ s⁻¹ for the CH₃OH and C₂H₅OH reactions, respectively. These results are in reasonable agreements with available experimental data except that of OH + C₂H₅OH in the high temperature range. The former reaction produces 96-89% of the H₂O + CH₂OH products, whereas the latter process produces 98-70% of H₂O + CH₃CHOH and 2-21% of the H₂O + CH₂CH₂OH products in the temperature range computed (200-3000 K).     

Synthesis of uranium complexes incorporating extended azo-imine ligands: Molecular and electronic structure

The new azo-imine ligands 2,4-di-tert-butyl-6-((2-((2-hydroxyphenyl)diazenyl) phenylimino)methyl)phenol, H₂L¹, 1a, and 2,4-di-tert-butyl-6-((2-((2-hydroxyphenyl) diazenyl)p-chlorophenylimino)phenol, H₂L², 1b, were prepared. Reaction of H₂L¹;1a, and H₂L²;1b, with uranyl nitrate hexahydrate afforded the mononuclear complexes of compositions [U(O)₂(L¹)(H₂O)]; 2a, and [U(O)₂(L²)(H₂O)]; 2b, complexes respectively. The newly synthesised ligands (1a and 1b) and the complexes (2a and 2b) were characterised unequivocally. The x-ray structure of 2a was determined. The tetradentate dianionic ligand (L¹)^2- coordinated the uranium ion equatorially with a water molecule in the same plane. Two axially coordinated oxo ligands completed the overall pentagonal bipyramid geometry around U(VI) ion. Structural pattern, electron transfer properties (oxidation near 1.32 ​V vs Ag/AgCl) and electronic transitions of [U(O)₂(L¹)(H₂O)]; 2a, and [U(O)₂(L²)(H₂O)]; 2b have been rationalized by DFT calculations.