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1.
金属镍吸附氢同位素的量子力学计算   总被引:18,自引:8,他引:10  
根据原子分子反应静力学与群论,确定了NiH、NiD和NiT的基电子状态为2Σ+。应用基函数6-311G和组态相关CI或QCISD方法,计算了氢同位素分子及其镍化物的能量E、定容热容Cv和熵S。设用总能量中的电子和振动能量近似代表NiH、NiD和NiT分子处于固态时的能量,用总熵中的电子和振动熵近似代表这些分子处于固态时的熵,进而计算了镍吸附H2、D2和T2分子过程的ΔH°、ΔS°、ΔG°和平衡压力,并导出它们与温度的函数关系。计算指出了同位素分子效应,结果合理。所以,本文所建议的用量子力学方法计算多相化学反应,有应用参考价值。  相似文献   

2.
在QCISD/6-331++(3df,3pd)水平上,优化出AlH2(X^2A1)分子稳定构型为C2v,其平衡核间距Re=1.592A、∠HAlH-118.68°,同时也计算出振动频率。在此基础上,根据微观可逆性原则,正确地判断了离解极限。使用多体项展式理论方法,导出了基态AlH2(C2v)平衡结构,然后根据势能函数等值图讨论了H+AlH反应和Al+H2反应的势能面静态特征。结果表明在H+AlH及  相似文献   

3.
在有效原子实势近似下, 采用Gaussian 98程序及B3LYP/SDD密度泛函方法计算得到了ZrCo和ZrCoH分子的结构及能量E、熵S. 在此基础上, 近似以气态分子总能量中的振动能Ev代替该分子处于固态时的振动能量, 以电子运动和振动运动熵Sev代替分子处于固态的熵, 计算了不同温度下固态ZrCo与H2, D2, T2反应的热力学函数ΔH, ΔG, ΔS及氢化反应平衡压力, 导出了氢化反应温度与平衡压力的依赖关系. 计算得出ZrCoH, ZrCoD, ZrCoT的生成焓(398-598 K)分别为82.81 , 81.54和80.49kJ/mol, 与实验结果很好符合.  相似文献   

4.
本文论述了电子-振动近似理论,并应用于TiH2、TiD2和TiT2基态3A2的计算,即用单个分子TiH2、TiD2和TiT2中的电子和振动能量和熵近似代表他们处于固态时的能量和熵,所得到的金属钛的氢化热力学函数ΔH0、ΔS0、ΔG0以及平衡压力与温度的关系,与文献符合很好.这表明电子振动近似理论的可应用性.计算方法为密度泛函理论B3P86/6-311G**.在此基础上进一步计算氢同位素在金属钛中的溶解度,结果合理.  相似文献   

5.
张莉  朱正和  杨本福  龙兴贵  罗顺忠 《物理学报》2006,55(10):5418-5423
根据原子分子反应静力学和群论,确定TiH2,TiD2和TiT2的基电子状态为3A2.应用基函数6-311G**和密度泛函理论B3P86方法,全电子计算了氢同位素分子及其钛化物的能量E、定容热容Cv和熵S.应用电子振动近似理论,即用单个分子TiH2,TiD2和TiT2中的电子和振动能量和熵近似代表他们处于固态时的能量和熵. 计算所得到的金属钛的氢化热力学函数ΔH0,ΔS0,ΔG0以及平衡压力与温度的关系,与文献符合很好,这表明电子振动近似理论的可应用性,选用金属钛作为中子靶是很正确的.  相似文献   

6.
用B3LYP/SDD密度泛函方法计算了CoH的微观性质、CoH(g)、CoD(g)和CoT(g)的能量 (E)和熵(S) ,进而计算Co与H2 、D2 、T2 反应的ΔH 、ΔG 、ΔS .CoH分子的基电子状态为三重态 ,Re、D 0 、ωe 分别为 1.5 2nm、2 77.84kJ/mol和 132 1cm-1,与实验值基本一致 .在固态分子的E和S的计算中 ,以气态分子计算得到的总能量中的振动能Ev 代替固态能量 ,以总熵中的电子振动熵SEv代替固态熵 .导出了Co与氢同位素气体反应的ΔH 、ΔG 、ΔS 及平衡氢压力与温度的关系 .CoH的室温下平衡离解压力很低 ,表明CoH是一种稳定的氢化物 ,这与CoH分子的D 0 很大的实验事实一致 .  相似文献   

7.
使用分子轨道从头算方法,对NaS和Na2S分子的基态几何构型和振动频率进行了理论研究。计算的结果表明,在HF/6—31和MP2/6—31G水平上,NaS分子的平衡键长和振动频率基本上是一致的。对于Na2S分子在上述M种水平上,线性结构是不稳定的,而弯曲结构是稳定的。电子关联作用把优化键角从161°(HF/6—31G)降低到111°[MP2(fu)/6—31G],这个变化可以用电子相关作用降低了Na—Na之间的Coulomb排斥来解释。对于NaS分子理论子言的键长是2.43。Na2S分子理论予言的键长是2.45,键角是111°。  相似文献   

8.
用密度泛函B3LYP方法、6-311 G基组对(ZnSe)n(n=1,2)分子体系进行了理论研究,得到(ZnSe)n(n=1,2)分子体系的基态电子状态的平衡几何Re、谐振频率、偶极矩和离解能De及不同温度、压力下的热力学函数值;设用总能量中的电子和振动能量近似代表ZnSe分子处于固态时的能量,用总熵中的电子和振动熵近似代表ZnSe分子处于固态时的熵,进而计算了Zn与Se反应的ΔH0、ΔS0、ΔG0,并由此计算出不同温度的反应平衡常数Kp.结果表明:在298~1150 K温度范围内,Zn与Se反应的自由能值均为负,且随着温度的升高,ΔG0值负的越多,表明在这个温度范围内反应能自发发生,而且自发趋势随温度的升高逐渐增大;平衡常数逐渐减小,即反应进行程度随温度的升高逐渐减小;ZnSe分子材料的导电性随压力增大而增强.  相似文献   

9.
李权  朱正和 《物理学报》2008,57(6):3419-3424
用密度泛函理论B3LYP方法计算研究AuZn和AuAl分子基态与低激发态的结构与势能函数,导出分子的光谱数据.结果表明,AuZn和AuAl分子基态分别为X2Σ和X1Σ,基态与低激发态的势能函数均可用Murrell-Sorbie函数来表达.AuZn分子低激发态a4Σ的绝热激发能为43529kJ/mol,AuAl分子低激发态a3Σ的绝热激发能为19991kJ/mol.计算固体AuZn和AuAl的内能和熵时,近似以气体分子的电子能和振动能代替固体分子的内能,用电子熵和振动熵代替固体分子的熵.在此近似下,计算得到AuZn和AuAl基态与低激发态固态分子生成反应热力学性质与温度的关系. 关键词: AuZn和AuAl B3LYP 热力学性质 势能函数  相似文献   

10.
应用原子分析反应静力学原理导出LaH分子的电子状态和可能的离解极限,考虑相对论紧致有效势PCEP(Relativistic Compact Effective Potential)近似下,用QCISD方法计算了LaH分子基态X^1Σ^+的平衡几何Re和离解能De为2.125A和2.623eV,并在计算出来的一系列背地里点势能基础上,用正规方程组拟合Murrell-Sorbie(M-S)势能函数,得  相似文献   

11.
Many steel structures can absorb varying amounts of hydrogen during manufacturing, processing such as electroplating or acid pickling and during service life by corrosion reactions or cathodic protection. Hydrogen is known to have a devastating effect on strength and ductility of iron and steel components. Many studies have been done on the detrimental effects of hydrogen on iron and different steel structures but there is a need for comprehensive research to cover all related parameters which can control the extent of hydrogen interaction and degradation in steels. In this review, at first hydrogen uptake and different damages associated with absorbed hydrogen in steels are discussed. Then, the effective parameters in the extent of hydrogen interaction and degradation, especially hydrogen embrittlement which is more common in steel components are reviewed.  相似文献   

12.
The natural abundance carbon-13 nuclear magnetic resonance spectra of diphenic acid and some 6-substituted dibenz [c,e] azepine, 5, 7-dione - which can be considered also as N-substituted diphenimide - were recorded using Fourier transform technique. The chemical shifts of various carbon resonance have been assigned on the basis of chemical shift theory, the signal multiplicity observed in the single frequency off-resonance decoupled (SFORD) spectra and comparison with the chemical shifts of the model compounds.  相似文献   

13.
栾伯晗  乔增熙  刘鹏  赵伟  鄂鹏  于达仁 《物理学报》2012,61(1):15202-015202
在新能源的研究中, 氢能成为与太阳能、风能等一样的绿色能源. 分数H原子是在某些特定催化物(如Ar+)的作用下, 基态H原子可以向比基态能级更低的分数主量子数能级跃迁, 同时释放出大量能量. 通过对氢氩等离子体H原子Balmerα 谱线超常展宽的规律性进行研究, 探讨这种伴随着大量能量释放的含H等离子体反应的存在性. 研究结果表明: 利用空心阴极放电管证实高能H原子的存在并首次发现超常展宽与氢氩配比的关系符合催化反应的特点; 通过比较研究的方法, 在实验上寻找加强含H等离子体反应的途径, 得到了更加清晰的H原子Balmerα 谱线超常展宽(半高展宽达到0. 245 nm). 关键词: 氢氩等离子体 H原子超常谱线展宽 氢能  相似文献   

14.
The study of the viability of hydrogen production as a sustainable energy source is a current challenge, to satisfy the great world energy demand. There are several techniques to produce hydrogen, either mature or under development. The election of the hydrogen production method will have a high impact on practical sustainability of the hydrogen economy. An important profile for the viability of a process is the calculation of energy and exergy efficiencies, as well as their overall integration into the circular economy. To carry out theoretical energy and exergy analyses we have estimated proposed hydrogen production using different software (DWSIM and MATLAB) and reference conditions. The analysis consolidates methane reforming or auto-thermal reforming as the viable technologies at the present state of the art, with reasonable energy and exergy efficiencies, but pending on the impact of environmental constraints as CO2 emission countermeasures. However, natural gas or electrolysis show very promising results, and should be advanced in their technological and maturity scaling. Electrolysis shows a very good exergy efficiency due to the fact that electricity itself is a high exergy source. Pyrolysis exergy loses are mostly in the form of solid carbon material, which has a very high integration potential into the hydrogen economy.  相似文献   

15.
Pipeline steels absorb different amounts of hydrogen during transportation of sour oil and gas. Since hydrogen-related damages such as hydrogen-induced cracking are strongly affected by hydrogen permeation behavior of steels, the purpose of this study determined to investigate hydrogen permeation behavior in API X-70 pipeline steel using electrochemical permeation method. The effect of heat treatment was also considered. It was found that hydrogen diffusivity increased by annealing the X-70 and it was decreased by normalizing. The condition was reverse for hydrogen apparent solubility. Finally, it was concluded that change in hydrogen diffusivity can be attributed to changes in grain size due to heat treatment.  相似文献   

16.
运用RH-402测氢仪测定具有高挥发性锂的铝-锂合金的固态氢含量具有相当难度。本文就如何鉴别体内氢和表面氢、如何选择加热功率和加热时间及试样大小做了大量探索实验,初步形成了可行的铝-锂固态氢含量的分析方法。同时就测量的误差来源及测氢过程中应注意之点进行了讨论。结果重复性好,且结果比较准确(利用俄罗斯铝-锂合金氢标样比较)。  相似文献   

17.
Strong solid state effects in low energy scattering of pμ atoms in solid hydrogen are reported and analyzed. Such effects have been observed in TRIUMF experiment E742 where muons are stopped in thin frozen (3 K) layers of hydrogen. Emission of low energy pμ atoms from the hydrogen layer into adjacent vacuum was much higher than expected, based on calculations which ignored the solid nature of hydrogen. Monte Carlo simulations, performed using the scattering cross-sections with solid state effects taken into account, show the important role of the coherent elastic Bragg scattering in the diffusion of pμ atoms. For pμ energies lower than the Bragg cut-off limit (∼2 meV) the total scattering cross-section falls by several orders of magnitude, the hydrogen target becomes transparent and the emission of cold pμ atoms takes place. This revised version was published online in August 2006 with corrections to the Cover Date.  相似文献   

18.
The existence of C–H···F–C hydrogen bonds in the complexes of trifluoromethane and cyclic molecule (oxirane, cyclobutanone, dioxane, and pyridine) has been experimentally proven by Caminati and co-workers. This study presents a theoretical investigation on these C–H···F–C hydrogen bonds at B97D/6-311++G** and MP2/6-311++G** levels, in terms of C–H vibrational frequency shifts, atoms in molecules characteristics, and the bonding feature of C–H···F–C hydrogen bonds. It is found that in three important aspects, there are significant differences in properties between C–H···F–C and conventional hydrogen bonds. The C–H···F–C hydrogen bonds show a blueshift in the C–H vibrational frequencies, instead of the X–H normal redshift in X–H···Y conventional hydrogen bonds. The natural bond orbital (NBO) analyses show that σ and p types of lone pair orbitals of the F atom to an antibonding σ*H–C orbital form a dual C–H···F–C hydrogen bond. Such a dual hydrogen bonding leads to the proton acceptor directionality of the C–H···F–C hydrogen bond softer. Our studies also show that the Laplacian of the electron density (▽2ρBCP) is not always a good criterion for hydrogen bonds. Therefore, we should not recommend the use of the Laplacian of the electron density as a criterion for C–H···F–C hydrogen bonds.  相似文献   

19.
孙继忠  李现涛  白净  王德真 《中国物理 B》2012,21(5):55205-055205
Hydrogen discharges driven by the combined radio-frequency(rf)/short pulse sources are investigated using the particle-in-cell method.The simulation results show that the discharge driven additionally by the short pulse can enhance the electron density and modulate the electron energy to provide a better condition for negative hydrogen ion production than the discharge driven by the rf-only source.  相似文献   

20.
Jesús Toribio 《哲学杂志》2015,95(31):3429-3451
Continuum modelling of hydrogen diffusion in metals, which accounts for both trapping and an imposed force field, is revisited. A generalised model of hydrogen diffusion and trapping is developed as a continuous interpretation of the discrete random-walk theory. A system of nonlinear equations describing the phenomenon of diffusion with multiple types of traps is derived without the assumption of a local equilibrium among hydrogen populations in dissimilar positions. Lattice-trap interchange kinetics can degenerate into local equilibrium as a limit case. Moreover, certain terms in general equations may be negligible in specific situations. By removing these terms, known particularised models of hydrogen diffusion and trapping are recovered. Determining the terms, which are disregarded in reduced models, enables a straightforward assessment of the applicability of these models. The advantages and limitations of particularised models applied to hydrogen embrittlement analyses are discussed.  相似文献   

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