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Real or Artificial Stability of ({text{CH}}_{5}^{ + }) Ions and Deuterated Variants ({mathbf{C}}{{{mathbf{H}}}_{x}}{mathbf{D}}_{{left( {5 - x} right)}}^{ + }) Based on Ab Initio Calculation and Rotational Spectrum ({text{CH}}_{5}^{ + }) 离子和氚化变体 ({mathbf{C}}{{{mathbf{H}}}_{x}}{mathbf{D}}_{{{left( {5 - x} right)}}^{ + }) 的真实或人为稳定性基于 Ab Initio 计算和旋转光谱
IF 0.7 4区 化学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2024-11-18 DOI: 10.1134/S0036024424702029
Majid Monajjemi,  Fatemeh Mollaamin

Protonated methane, ({text{CH}}_{5}^{ + }), has unusual vibrational and rotational behavior because its three nonequivalent equilibrium structures have nearly identical energies and its five protons scramble freely. The highly flexible ({text{CH}}_{5}^{ + }), molecular ion has been shown by ab initio calculations to have 120 symmetrically equivalent minima of Cs symmetry in its ground electronic state. Complete proton rearrangement, making all minima accessible to each other, is possible as a result of two large-amplitude internal motions: an internal rotation about the C3 axis with an ab initio barrier of 30 cm–1 and an internal flip motion with an ab initio barrier of 300 cm–1 that exchanges protons between the H2 and ({text{CH}}_{3}^{ + }) groups. We calculate the structure of the J =( leftarrow )1 and 1 ( leftarrow ) 0 rotational transitions of ({text{CH}}_{5}^{ + }), ({text{CD}}_{5}^{ + }) and also other variants containing ({text{C}}{{{text{H}}}_{x}}{text{D}}_{{(5 - x)}}^{ + }). Although many theoretical papers have been published on the quantum mechanics of these systems, a better understanding requires spectral and conformational analysis. Post Hartree-Fock, Møller-Plesset and DFT calculation with the correlation consistent polarized valence double and triple zeta basis sets have done for the zero-point energies of ({text{C}}{{{text{H}}}_{x}}{text{D}}_{{(5 - x)}}^{ + }). The present results indicates the mode 8, 12, and 10 agree with qualitative of ({text{CH}}_{5}^{ + }), which is highly fluxional and has a complex spectrum while the C–X bonds which are broken and reformed all the time. The spectrum of mode 12 is highly complex with huge red-and some blue shifts. In particular, they can be attributed to the rapid coupling of the original CH-stretching normal mode to motions more closely related to isomerization, i.e., bending or rocking. There has thus been a long debate whether ({text{CH}}_{5}^{ + }) has a structure at all or not and is it real rotational motions or artificial. In addition, we include the contribution to the torsional barrier from the zero point energies of the other (high-frequency) vibrations, the effect of centrifugal distortion, and the effect of second-order rotation-vibration interactions.

质子化甲烷(({text{CH}}_{5}^{ + }) 具有不寻常的振动和旋转行为,因为它的三个非等效平衡结构具有几乎相同的能量,而且它的五个质子可以自由扰动。高度灵活的 ({{CH}}_{5}^{ + }) 分子离子已被 ab initio 计算证明在其基态电子态中有 120 个对称等效的 Cs 对称极小值。由于两个大振幅的内部运动:一个是围绕 C3 轴的内部旋转运动,ab initio 障碍为 30 cm-1;另一个是在 H2 和 ({text{CH}}_{3}^{ + }) 基团之间交换质子的内部翻转运动,ab initio 障碍为 300 cm-1。我们计算了 ({text{CH}}_{{5}^{ + }) 的 J = 2 (左箭头)1 和 1 (左箭头)0 旋转转变的结构、({text{CD}}_{5}^{+})以及包含 ({{C}}{{{H}}}_{x}}{text{D}}_{{(5 - x)}}^{ + }) 的其他变体。虽然关于这些系统的量子力学的理论论文已经发表了很多,但要更好地理解它们,还需要进行光谱和构象分析。后哈特里-福克、默勒-普莱歇特和 DFT 计算使用了相关一致的极化价双倍和三倍泽塔基础集,对 ({text{C}}{{{text{H}}}_{x}}{text{D}}_{{(5 - x)}}^{ + }) 的零点能量进行了计算。目前的结果表明,模式 8、12 和 10 与 ({text{CH}}_{5}^{ + }) 的定性一致,后者具有高度的通量和复杂的光谱,而 C-X 键一直在断裂和重构。模式 12 的光谱非常复杂,具有巨大的红移和一些蓝移。特别是,它们可归因于原始 CH 拉伸正常模式与与异构化(即弯曲或摇摆)更密切相关的运动的快速耦合。因此,关于 ({{CH}}_{5}^{ + }) 是否具有结构以及它是真实的旋转运动还是人为的旋转运动的争论由来已久。此外,我们还考虑了其他(高频)振动的零点能量对扭转障碍的贡献、离心变形的影响以及二阶旋转振动相互作用的影响。
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引用次数: 0
Surface Tension and Adsorption at the Vapor–Liquid Interface in a Methane–Ethane System 甲烷-乙烷体系中蒸汽-液体界面的表面张力和吸附力
IF 0.7 4区 化学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2024-11-18 DOI: 10.1134/S0036024424702066
D. Yu. Lenev, S. A. Zakharov, V. V. Pisarev

Molecular dynamics is used to calculate the vapor–liquid equilibrium and liquid–vapor surface tension for a methane–ethane system. Good agreement of the parachor value for ethane between the molecular model and experimental data is shown for the 203–253 K range of temperatures and pressures up to 60 atm. The dependence of the surface tension of the mixture on pressure in the range of 4–40 atm at a temperature of 213 K shows a drop in both the surface tension and the difference in densities between the liquid and vapor as the pressure rises and approaches the critical locus. Approximating the density profiles obtained for the same conditions, it is concluded that the width of the interphase boundary also grows. The amount of methane adsorbed on the surface of the liquid film is calculated. The dependence of the molar adsorption of methane on the difference between the densities of the components in the liquid and gas phases is obtained, along with its analytical expression in the context of the Gibbs theory. Features of the approach that is used include no need for approximations of the ideal gas or the ideal solution, and the use of only experimentally obtained data as input. The resulting values of methane adsorption are in good agreement with the derived analytical dependence.

分子动力学用于计算甲烷-乙烷体系的汽液平衡和液汽表面张力。在 203-253 K 的温度和高达 60 atm 的压力范围内,分子模型与实验数据之间的乙烷降落数值显示出良好的一致性。在温度为 213 K、压力为 4-40 atm 的范围内,混合物的表面张力与压力的关系显示,随着压力的升高和临界点的接近,表面张力和液体与蒸汽之间的密度差都有所下降。通过对相同条件下获得的密度曲线进行近似分析,可以得出结论:相间边界的宽度也在增加。计算了液膜表面的甲烷吸附量。得出了甲烷摩尔吸附量与液相和气相中各组分密度差的关系,以及其在吉布斯理论中的分析表达式。所使用方法的特点包括无需对理想气体或理想溶液进行近似,以及仅使用实验获得的数据作为输入。由此得出的甲烷吸附值与推导出的分析依赖关系非常吻合。
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引用次数: 0
Effect of Graphene Oxide on the Permeability of Asymmetric Polysulfone Membranes 氧化石墨烯对不对称聚砜膜渗透性的影响
IF 0.7 4区 化学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2024-11-18 DOI: 10.1134/S0036024424702236
A. S. Gizzatov, M. A. Petrov, Yu. S. Eremin, A. M. Grekhov

Membranes have been prepared from polysulfone and graphene oxide with mass concentrations from 0 to 0.4%. A series of experiments were conducted to study the permeability of the obtained samples at pressures of 10, 15, and 20 atm. The experimental time dependences of the permeated water volume at a constant pressure were obtained. The dependence of the membrane permeability on the graphene oxide concentration and pressure was calculated. Conclusions were drawn about the influence of graphene oxide concentration and pressure on the permeability of the samples.

用聚砜和氧化石墨烯制备了质量浓度为 0% 至 0.4% 的薄膜。为了研究获得的样品在 10、15 和 20 atm 压力下的渗透性,进行了一系列实验。实验得出了恒定压力下渗透水量的时间相关性。计算了膜渗透性与氧化石墨烯浓度和压力的关系。得出了氧化石墨烯浓度和压力对样品渗透性影响的结论。
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引用次数: 0
Experimental Data and Thermodynamic Modeling of Solid–Liquid and Liquid–Vapor Equilibria in the CO2 + Ethanol + Acetaminophen System 二氧化碳+乙醇+对乙酰氨基酚体系中固液和液汽平衡的实验数据和热力学模型
IF 0.7 4区 化学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2024-11-18 DOI: 10.1134/S0036024424701929
J. V. Mattos, M. J. Molina, S. B. Rodriguez-Reartes, L. Ferreira-Pinto, M. S. Zabaloy, P. F. Arce, L. Cardozo-Filho

In this study, experimental carry out of liquid–vapor and solid–liquid phase transitions were conducted for the ternary system {CO2 (1) + ethanol (2) + acetaminophen (3)} at different concentrations of paracetamol in ethanol for temperatures from 313 to 333 K and pressures up to 12 MPa. Experimental high pressure phase transition data were obtained using the static method in a variable volume view cell. Experimental data were compared with the literature for systems containing acetaminophen in a saturated solution. The presence of paracetamol in the binary system {CO2 (1) + ethanol (2)} significantly alters the behavior of the phase under the conditions of temperature and concentration studied. It was observed that in the ternary system {CO2 (1) + ethanol (2) + acetaminophen (3)} with a saturated solution at the lowest temperature, 313 K, CO2 acts as a cosolvent for mole fractions lower than 0.6. Thermodynamic simulations employing the Perturbed Chain Statistical Associating Fluid Theory (PC-SAFT) Equations of State (EoS) aligned the experimental results adequately. The observed minimal deviations in pressure and temperature validate the efficacy of the thermodynamic models applied in this study.

本研究针对乙醇中不同浓度的扑热息痛在温度为 313 至 333 K、压力高达 12 MPa 的三元体系 {CO2 (1) + 乙醇 (2) + 对乙酰氨基酚 (3)} 进行了液-气相和固-液相转变实验。高压相变实验数据是在可变容积观察池中采用静态方法获得的。实验数据与文献中含有对乙酰氨基酚的饱和溶液体系进行了比较。在所研究的温度和浓度条件下,对乙酰氨基酚在二元体系 {CO2 (1) + 乙醇 (2)} 中的存在极大地改变了相的行为。研究观察到,在最低温度 313 K 饱和溶液的三元体系 {CO2 (1) + 乙醇 (2) + 对乙酰氨基酚 (3)} 中,二氧化碳在分子分数低于 0.6 时充当共溶剂。采用扰动链统计关联流体理论(PC-SAFT)状态方程(EoS)进行的热力学模拟与实验结果充分吻合。观察到的压力和温度的最小偏差验证了本研究中应用的热力学模型的有效性。
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引用次数: 0
The Use of Isotopic Exchange in Molecular Hydrogen to Study the Physicochemical Properties of Bimetallic Nanoparticles 利用分子氢中的同位素交换研究双金属纳米粒子的物理化学特性
IF 0.7 4区 化学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2024-11-18 DOI: 10.1134/S0036024424702170
M. B. Pshenitsyn, O. A. Boeva

The catalytic and adsorption properties of supported mono- and bimetallic nanoparticles of the copper–silver and copper–gold systems were studied. The particle sizes were 5–9 nm. The catalytic properties of the samples were studied at 77 K in deuterium–hydrogen exchange reactions and ortho-to-para conversion of protium. A comparison of the obtained data on the catalytic properties of the samples in isotope exchange reactions in molecular hydrogen and ortho-to-para conversion of protium showed that the mono- and bimetallic nanoparticles of the systems have magnetic properties. A comparison of the activities of the mono- and bimetallic systems in the deuterium–hydrogen exchange reaction revealed a more significant synergistic effect for the copper–gold system relative to the copper–silver system, which is explained by the greater difference between the electronegativities of atoms in the systems.

研究了铜-银和铜-金体系的单金属和双金属纳米颗粒的催化和吸附特性。颗粒大小为 5-9 纳米。研究了这些样品在 77 K 下进行氘氢交换反应和氕氘正向转化时的催化特性。对样品在分子氢同位素交换反应和氕氕钡正钡转换反应中的催化特性数据进行比较后发现,系统中的单金属和双金属纳米粒子都具有磁性。通过比较单金属和双金属体系在氘氢交换反应中的活性,发现铜-金体系比铜-银体系具有更显著的协同效应,这是因为体系中原子的电负性差异更大。
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引用次数: 0
The Second Law of Thermodynamics and the Surface Characteristics of Dispersed Systems 热力学第二定律与分散系统的表面特性
IF 0.7 4区 化学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2024-11-18 DOI: 10.1134/S0036024424702078
Yu. K. Tovbin

An analysis of the literature shows that all surface characteristics of dispersed systems (surface tensions, contact angles, disjoining pressure, and the properties of small systems) have ambiguous thermodynamic definitions. The second law of Clausius thermodynamics, which requires additional experimental data on the periods of relaxation of momentum, energy, and mass transfer processes, is used to eliminate this ambiguity.

对文献的分析表明,分散系统的所有表面特征(表面张力、接触角、分离压力和小系统的特性)在热力学定义上都存在模糊性。克劳修斯热力学第二定律需要关于动量、能量和质量传递过程弛豫期的额外实验数据,该定律用于消除这种模糊性。
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引用次数: 0
Thermodynamic Modeling of the Ag–Al–In System 银-铝-铟体系的热力学模型
IF 0.7 4区 化学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2024-11-18 DOI: 10.1134/S0036024424701917
V. A. Lysenko

Thermodynamic models of liquid and ternary solid solutions in the Ag–Al–In system are constructed on the basis of available experimental information. These models and ones of other phases of this system known in the literature are used to determine the coordinates of invariant points of the Ag–Al–In system and a projection of its liquidus surface. Polythermal cross sections of the phase diagram of this system are calculated for compositions xAl/xIn = 4.255, xIn/xAl = 2.096, and xAg/xIn = 1.064, along with isothermal cross sections at 973 and 573 K.

根据现有的实验信息,构建了银-铝-铟体系中液态和三元固态溶液的热力学模型。这些模型和文献中已知的该体系其他相的模型被用来确定 Ag-Al-In 体系不变点的坐标及其液面的投影。计算了 xAl/xIn = 4.255、xIn/xAl = 2.096 和 xAg/xIn = 1.064 成分下该体系相图的多热截面,以及 973 和 573 K 时的等温截面。
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引用次数: 0
Developing the Isotopic Technique of Studying Diffusion in Metals 开发研究金属扩散的同位素技术
IF 0.7 4区 化学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2024-11-18 DOI: 10.1134/S003602442470211X
I. M. Rumyantsev, V. A. Kashcheev, V. I. Petrov, A. N. Shabalin

The authors study the experimental conditions for determining the diffusion mobility of impurities in solid bodies. Considering these conditions shows the need to continue developing the familiar Gruzin technique. In studying a large group of elements in metallic beryllium, Gladkov’s research group analyzed the effects of refining, which includes the absorption of radiation of an isotope by a sample and the dynamics of changes in the source in the process of diffusion annealing. Mathematical tools for considering these effects are developed. It is concluded that the new ways of processing the experimental results can be used in studying the diffusion characteristics of a wide range of contaminants in solid matrices.

作者研究了确定固体杂质扩散流动性的实验条件。对这些条件的考虑表明,有必要继续发展我们熟悉的格鲁津技术。在研究金属铍中的一大类元素时,格拉德科夫研究小组分析了精炼的影响,其中包括样品对同位素辐射的吸收以及扩散退火过程中源的动态变化。开发了考虑这些影响的数学工具。结论是,处理实验结果的新方法可用于研究固体基质中各种污染物的扩散特性。
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引用次数: 0
Characteristics and Magnetic Properties of Carbon-Coated Cobalt Nanoparticles Deposited on Silica 沉积在二氧化硅上的碳包钴纳米粒子的特性和磁性能
IF 0.7 4区 化学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2024-11-18 DOI: 10.1134/S0036024424702030
P. A. Chernavskii, S. V. Maksimov, G. V. Pankina, R. Yu. Novotortsev, A. V. Shumiytsev, S. I. Panfilov, A. A. Novakova, O. L. Eliseev

Cobalt nanoparticles embedded in a carbon matrix were obtained by thermolysis of glucose deposited on Co3O4/SiO2. The magnetic characteristics of the obtained nanoparticles were measured. This process formed single-domain (d < 20 nm) carbon-coated Co nanoparticles. The average size and the size distribution of Co nanoparticles depend on the amount of glucose used for the preparation. The use of a relatively small amount of glucose (glucose/cobalt < 1 mol/mol) leads to the formation of carbon shells enveloping Co nanoparticles, which are resistant to oxidation in air up to 200°C. In contrast, the use of a larger amount of glucose leads to the formation of an amorphous carbon layer with metal particles enclosed in it. Thus, the resulting nanoparticles are more susceptible to oxidation, and approximately half of the deposited cobalt is oxidized to CoO within a few days of exposure to air.

通过热解沉积在 Co3O4/SiO2 上的葡萄糖,获得了嵌入碳基质中的钴纳米粒子。测量了所获纳米粒子的磁特性。这一过程形成了单域(d < 20 nm)碳包覆 Co 纳米粒子。Co 纳米粒子的平均尺寸和尺寸分布取决于制备过程中使用的葡萄糖量。使用相对较少的葡萄糖(葡萄糖/钴 < 1 mol/mol)会形成包覆 Co 纳米粒子的碳壳,这种碳壳在高达 200°C 的空气中具有抗氧化性。相反,使用较多的葡萄糖则会形成无定形碳层,其中包裹着金属颗粒。因此,生成的纳米粒子更容易被氧化,大约一半的沉积钴在暴露于空气中几天后就会被氧化成 CoO。
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引用次数: 0
Mass Transfer and Fluctuations in the Root-Mean-Square Density of Molecules around the Critical Point 临界点附近的质量传递和分子的均方根密度波动
IF 0.7 4区 化学 Q4 CHEMISTRY, PHYSICAL Pub Date : 2024-11-18 DOI: 10.1134/S0036024424702017
E. V. Votyakov, Yu. K. Tovbin

The authors calculate the concentration dependence of the coefficient of mass transfer and mean-root-square fluctuations of attracting molecules under sub- and supercritical conditions for different approximations of cluster variation (CV) that allow for indirect correlations. The simplest lattice structure is considered: a uniform flat face (100) that provides an exact solution to the problem of multiple bodies. A comparison is given of characteristics calculated for a series of simplest CVM basis clusters (2 × n, n = 2–5, 3 × 3, 3 × 4) and a quasi-chemical approximation (cluster 2 × 1) that reflects only the effects of direct correlations. The coefficient of mass transfer is calculated within the theory of the absolute reactions rates of nonideal reaction systems. The effects the dependence of the motion of molecules has upon attraction from the side of neighboring molecules that block an available volume for movements on root-mean-square fluctuations are discussed. It is shown that a region near (above and below) the critical point can be selected in which there is an abrupt drop in the coefficient of diffusion because of large fluctuations of the material’s density. The increased accuracy of indirect correlations expands the area of thermodynamic parameters responsible for hindering mass transfer. The concept of transcritical first-order phase transitions and its relationship to the effects of kinetic resistivity to mass transfer are discussed.

作者计算了亚临界和超临界条件下吸引分子的传质系数和均方根波动的浓度依赖性,以及允许间接相关性的不同簇变化(CV)近似值。我们考虑了最简单的晶格结构:均匀平面 (100),它提供了多体问题的精确解决方案。比较了一系列最简单的 CVM 基簇(2 × n、n = 2-5、3 × 3、3 × 4)和仅反映直接相关影响的准化学近似(簇 2 × 1)计算的特征。传质系数是根据非理想反应系统的绝对反应速率理论计算得出的。讨论了分子运动对相邻分子侧吸引的依赖性,相邻分子侧吸引阻挡了均方根波动的可用运动体积。研究表明,可以选择临界点附近(高于和低于临界点)的一个区域,在该区域内,由于材料密度的大幅波动,扩散系数会突然下降。间接相关性精度的提高扩大了阻碍传质的热力学参数的范围。本文讨论了跨临界一阶相变的概念及其与动力学电阻率对传质影响的关系。
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引用次数: 0
期刊
Russian Journal of Physical Chemistry A
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