常压下固态KNO2热力学性质的密度泛函理论研究

采用密度泛函理论结合准谐德拜模型研究常压下300~725 K间KNO₂立方结构的热力学性质,重点分析常压下定压热容、定容热容、熵、德拜温度、体膨胀系数、平衡体积和体弹模量随温度的变化.结果显示,常压下计算的定压热容随温度的变化与实验数据符合较好,而计算的熵与实验数据相差较大.计算得到KNO₂的平均体膨胀系数约为1.837 8×10^-5K^-1,常温下(300 K)KNO₂的德拜温度约为667.13K.     

Ar/CH4等离子体射流发射光谱诊断研究

为了更加深入的研究大气压条件下Ar/CH₄等离子体射流的放电机理和其内部电子的状态,通过自主设计的针-环式介质阻挡放电结构,在放电频率10 kHz、一个大气压条件下产生了稳定的Ar/CH₄等离子体射流,并利用发射光谱法对其进行了诊断研究。对大气条件下Ar/CH₄等离子体射流的放电现象及内部活性粒子种类进行诊断分析,重点研究了不同氩气甲烷体积流量比、不同峰值电压对大气压Ar/CH₄等离子体射流电子激发温度、电子密度以及CH基团活性粒子浓度的影响规律。结果表明,大气压条件下Ar/CH₄等离子体射流呈淡蓝色,在射流边缘可观察到丝状毛刺并伴有刺耳的电离声同时发现射流尖端的形态波动较大;通过发射光谱可以发现Ar/CH₄等离子体射流中的主要活性粒子为CH基团,C,CⅡ,CⅢ,CⅣ,ArⅠ和ArⅡ,其中含碳粒子的谱线主要集中在400~600 nm之间,ArⅠ和ArⅡ的谱线分布在680~800 nm之间;可以发现CH基团的浓度随峰值电压的增大而增大,但CH基团浓度随Ar/CH₄体积流量比的增大而减小,同时Ar/CH₄等离子体射流中C原子的浓度随之增加,这表明氩气甲烷体积流量比的增大加速了Ar/CH₄等离子体射流中C-H的断裂,因此可以发现增大峰值电压与氩气甲烷体积流量比均可明显的加快甲烷分子的脱氢效率,但增大氩气甲烷体积流量比的脱氢效果更加明显。通过多谱线斜率法选取4条ArⅠ谱线计算了不同工况下的电子激发温度,求得大气压Ar/CH₄等离子体射流的电子激发温度在6 000~12 000 K之间,且随峰值电压与氩气甲烷体积流量比的增大均呈现上升的趋势;依据Stark展宽机理对Ar/CH₄等离子体射流的电子密度进行了计算,电子密度的数量级可达1017 cm-3,且增大峰值电压与氩气甲烷体积流量比均可有效的提高射流中的电子密度。这些参数的探索对大气压等离子体射流的研讨具有重大意义。     

Ar离子注入YBa2Cu3O7-x超导薄膜中微结构变化的透射电子显微镜研究

Ar离子注入YBa₂Cu₃O_7-x超导薄膜后,不仅会引起样品超导转变温度T_c和临界电流密度J_c的下降,还会使样品的正常态由金属型变为半导体型。透射电子显微镜观察发现在小剂量(<5×10¹²Ar/cm²)注入情况下,样品的晶格结构几乎不受影响。随着注入剂量的增加,晶格损伤越来越严重,最终变成非晶态。对实验结果的分析表明,Ar离子注入引起YBa_{2< 关键词：}     

利用微扰理论计算实际气体比定容热容

本文以统计热力学中的BH微扰理论为基础,建立了一种推算实际气体比定容热容的方法。用这种方法对20余种实际气体在饱和线上和气相区的比定容热容进行了推算。计算结果表明,本文方法能推算普通气体、氟利昂类气体、烷烃类气体的比热容,在饱和线上推算的平均相对偏差为1.10%,过热区为1.46%,最大相对偏差不超过6%。     

微波激励ArS2体系机理的探讨

采用ab initio MP2/6-31+G方法计算了ArS₂体系分析势能函数.并在此基础上, 对Ar+S₂的非反应动力学过程进行了研究.结果表明,Ar与S₂的结合 为很弱的物理吸附,其间没有化学键生成.在所计算的能量范围,Ar与S₂的动力 学过程主要是非弹性碰撞.通过对非弹性碰撞产物的分析,结果显示Ar原子对S₂ 基态(X³Σ^-_g 关键词： 2')" href="#">ArS₂ 分析势能函数 反应动力学 碰撞激发     

声弛豫过程影响下的气体平衡态热容合成方法及其在气体检测中的应用

声扰动形成的分子振动弛豫过程使得气体热容成为依赖于声频率的有效热容,导致随频率变化的声速频散和声弛豫吸收。本文基于单弛豫过程合成算法,提出一种基于两频点声速和声吸收测量值的气体平衡态热容合成方法。该方法两个测量声频点只需在声弛豫吸收显著的频率范围即可分别合成可激发气体分子内外自由度热容,并有效消除声弛豫过程对气体平衡态热容测量结果的影响。对于室温下由CO₂、CH₄、Cl₂、N₂和O₂组成的多种气体,合成的气体热容值与基于Planck-Einstein公式的热力学理论计算结果相符,相比实验数据最大相对误差为3.51%。合成的转动和振动热容还可应用于气体分子几何结构、振动频率大小和混合气体摩尔分数的检测。      

高压下TiAl3结构及热动力学性质的第一性原理研究

采用平面波赝势密度泛函理论研究了钛铝系金属间化合物TiAl₃的结构性质, 计算值与实验值及其他理论值相符合. 通过准谐德拜模型研究了TiAl₃的热动力学性质, 计算得到了相对体积(V/V₀)与压强和温度的关系, 以及不同温度和压强下的热膨胀系数和热容. 与TiAl的计算结果进行对比, 发现随着温度的升高, TiAl的热膨胀系数增大的速度高于TiAl₃, 且随着压强的增大温度效应减弱; TiAl₃的热容值近似为TiAl的热容值的2倍. 关键词： 结构性质 热动力学性质 第一性原理 高压     

K0.3MoO3和Tl0.3MoO3派尔斯相变临界行为的比热研究

采用连续绝热加热法测量了K_0.3MoO₃和Tl_0.3MoO₃在100—220K温度范围内的比热。发现K_0.3MoO₃和Tl_0.3MoO₃分别在177.5K和172.3K发生派尔斯相变。对派尔斯相变附近比热临界行为的研究表明,K_0.3MoO₃和Tl_0.3MoO₃的临界区域宽度分别为6K和8K,临界行为属于三维XY模型普适类。 关键词：     

1MeV Si+衬底加温注入Al0.3Ga0.7As/GaAs超晶格和GaAs的晶格损伤研究

用卢瑟福背散射／沟道技术研究了１ＭｅＶＳｉ⁺在衬底加温和室温下以不同剂量注入Ａｌ_0.3Ｇ_0.7Ａｓ／ＧａＡｓ超晶格和ＧａＡｓ后的晶格损伤。在衬底加温下，观察到Ａｌ_0.3Ｇａ_0.7Ａｓ／ＧａＡｓ超晶格和ＧａＡｓ都存在一个动态退火速率与缺陷产生速率相平衡的剂量范围，以及两种速率失去平衡的临界剂量。超晶格比ＧａＡｓ更难以损伤，并且它的两种速率失去平衡的临界剂量也大于ＧａＡｓ中的相应临界剂量，用热尖峰与碰撞模型解释了晶格损伤积累与注入剂量和衬底温度的关系。用ＣＮＤＯ／２量子化学方法计算了ＧａＡｓ和Ａｌ_xＧａ_1-xＡｓ中化学键的相对强度，并根据计算结果解释了注入过程中Ａｌ_0.3Ｇａ_0.7Ａｓ／ＧａＡｓ超晶格和ＧａＡｓ中晶格损伤程度的差别。 关键词：     

跨临界CO2热泵空调系统仿真优化研究

为了研究跨临界CO₂热泵空调系统在不同工况下的制热性能,应用MATLAB软件,对带回热器的跨临界CO₂系统进行仿真研究。针对系统内排气压力P_cond、蒸发温度T_evp、气冷器排气温度T_out、过热度ΔT等因素,探究其对系统制热COP的影响。研究结果表明：T_evp、ΔT每升高1℃,系统COP分别上升5%～7%、0.1%～1.3%;T_out每增加1℃,系统COP降低0.17～0.04。通过仿真研究得出,跨临界CO₂系统的最优排气压力P_cond＿opt,并拟合得到其计算关联式。     

Heat capacity investigation of dopant effects on the magnetic disordering temperature in Fe3O4†

The heat capacities of ZnFe₂O₄, Zn_0.005Fe_2.995O₄, Zn_0.066Fe_2.934O₄, and Cd_0.010Fe_2.990O₄ were measured over the temperature range of 350–1000 K by means of differential scanning calorimetry. The temperatures at which the maximum in heat capacity occurs due to the ferrimagnetic anomaly in the doped-Fe₃O₄ samples were found to decrease with increasing dopant. The excess entropy associated with the ferrimagnetic anomaly was estimated using three methods. One method, used previously for Fe₃O₄, employed a calculated lattice contribution for Fe₃O₄. The other two methods used the experimentally determined heat capacity of ZnFe₂O₄, either unmodified or mass adjusted, to approximate contributions from lattice vibrations.     

A molecular dynamics study on the role of attractive and repulsive forces in excess heat capacity at constant volume of dense fluids

The curves of experimental heat capacity against density show a minimum around and below the critical temperature (Tc), but at higher temperatures, this minimum is not observed. In this study, the role of attractive and repulsive forces on excess heat capacity of Lennard–Jones (LJ) dense fluids has been investigated using a molecular dynamics simulation technique. LJ potential is divided into attractive and repulsive parts. From the molecular dynamics calculations, potential energy and heat capacities have been obtained for Argon at temperatures of 100–500?K. The repulsive forces play the main role in causing the heat capacities at temperatures greater than critical point. Around and below the critical temperature, the role of repulsion is dominant at high densities, but attraction has the main role at low densities, consequently at middle densities, a minimum is formed.     

The use of densimetry and fixed-cell scanning calorimetry to probe solute and solution structure and reactions from 270 K to 400 K

We have used a vibrating-tube densimeter to investigate the densities and volumetric properties of aqueous solutions, and a fixed-cell scanning calorimeter to measure aqueous solution heat capacities. Solutions investigated include sugars, neutral weak acids and bases, neutralized acids and bases, neutral and protonated amino acids, surfactants, and both strong and ion-paired electrolytes. We have made measurements at molalities m from 0.005 mol·kg⁻¹ to 0.5 mol·kg⁻¹, at temperatures T from 278.15 K to 393.15 K, and at the pressure P = 0.35 MPa. We have calculated the apparent molar volumes V_φ and apparent molar heat capacities C_p,φ of the solutions and fit them by regression to equations that describe the surfaces (V_φ, T, m) and (C_p,φ, T, m). These results reflect changes and differences in both solute-solute and solute-solvent interactions. Standard state partial molar volumes V₂° and heat capacities C_p,2° were estimated by extrapolation to the M = 0 mol·kg⁻¹ plane of the fitted surfaces. We have calculated (Δ_r,C_p,m, T, m) surfaces for various proton dissociation reactions, and we have created surfaces representing (Δ_rH_m, T, m) and (pQ_a, T, m) by integration of our (Δ_rC_p,m, T, m) surfaces using values for (Δ_rH_m, m) and (pK_a, m) at a reference T as integration constants. We have also created surfaces representing (Δ_rS_m, T, m) and (Δ_rV_m, T, m) for these dissociation reactions.     

Heat capacities of Laves phase compounds RMn2 (R = Y, Gd and Er)

Measurements of heat capacity indicate that the Mn moment in YMn₂ has an itinerant character and an additional C_M is observable even above T_N. In GdMn₂, the Gd moments are in disorder at T_N simultaneously with the Mn moments. The CEF contributions in ErMn₂ are observed and are calculated using a single-ion Hamiltonian.     

First-principles study of the elastic and thermodynamic properties of thorium hydrides at high pressure

The high pressure behaviors of Th_4H_(15) and ThH_2 are investigated by using the first-principles calculations based on the density functional theory(DFT). From the energy–volume relations, the bct phase of ThH_2 is more stable than the fcc phase at ambient conditions. At high pressure, the bct ThH_2 and bcc Th_4H(15) phases are more brittle than they are at ambient pressure from the calculated elastic constants and the Poisson ratio. The thermodynamic stability of the bct phase ThH_2 is determined from the calculated phonon dispersion. In the pressure domain of interest, the phonon dispersions of bcc Th_4H(15) and bct ThH_2 are positive, indicating the dynamical stability of these two phases, while the fcc ThH_2 is unstable. The thermodynamic properties including the lattice vibration energy, entropy, and specific heat are predicted for these stable phases. The vibrational free energy decreases with the increase of the temperature, and the entropy and the heat capacity are proportional to the temperature and inversely proportional to the pressure. As the pressure increases, the resistance to the external pressure is strengthened for Th_4H_(15) and ThH_2.     

ZrV2结构、弹性和热力学性质的第一性原理计算

采用基于密度泛函理论的第一性原理平面波赝势方法研究ZrV₂的晶体结构和弹性,利用准谐Debye模型计算在不同温度(T=0~1200 K)和不同压强(P=0~20 GPa)下ZrV₂的热力学性质,包括弹性模量与压强,热熔与温度,以及热膨胀系数与温度和压力的关系.结果表明:计算的ZrV₂晶格常数与实验值符合较好,晶体材料的弹性常数随着压力增加而增加;在一定温度下,相对体积、热熔随着压强的增加而减小,德拜温度、弹性模量随着压强的增加而增加,且高压下温度对ZrV₂热膨胀系数的影响小于压强的影响.     

高压下ErNi2B2C弹性性质、电子结构和热力学性质的第一性原理研究

采用密度泛函理论中的赝势平面波方法研究了高压下超导材料 ErNi₂B₂C 的弹性性质、电子结构和热力学性质.分析表明, 弹性常数、体弹模量、剪切模量、杨氏模量和弹性各向异性因子的外压力效应明显. 电子态密度(DOS)的计算结果显示, 在费米能级(E_F)处的 DOS 峰随外界压强的增大显著降低, 由于 ErNi₂B₂C 相对较高的超导温度(T_c)起因于E_F处的 DOS 峰, 因此推测压强增大可能会降低 ErNi₂B₂C 的 T_c.类似的现象在超导材料 MgB₂和 SrAlSi 中已被发现.此外, 基于准谐德拜模型, 对 ErNi₂B₂C 在高温高压下的热力学性质的研究表明, 在一定范围内, 温度和压强将对其热膨胀系数和热容产生明显的影响. 关键词： 高压 弹性性质 电子结构 热力学性质