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课程名称:物理化学 - 固态 课程概述: 固体具有确定的质量、体积和形状,这源于其组成粒子的位置固定、距离较短以及粒子间的强相互作用。非晶态固体的组成粒子仅呈现短程有序,因此它们表现得像冷却的液体,没有明确的熔点且性质各向同性。而在晶态固体中,组成粒子的排列具有长程有序,表现出明显的熔点,各向异性,并且其粒子形状具有特征。晶态固体的性质依赖于组成粒子之间的相互作用,根据这个基础,可以将其分为分子固体、离子固体、金属固体和共价固体四个类别,它们的性质差异很大。 在晶态固体中,组成粒子按照规则的模式排列,这种排列通常用三维点阵图表示,称为晶格。每个晶格点代表空间中一个粒子的位置。共有十四种不同类型的晶格,称为布拉维晶格。每个晶格可以通过重复其小的特征部分(称为单元胞)生成。单元胞通过其边长和三个夹角来表征,可以是原始的(仅在角落位置有粒子)或中心型(在体心、面心或两相对面中心有额外粒子)。 粒子的紧密堆积形成两种高效的晶格,六方密堆积(hcp)和立方密堆积(ccp),后者也称为面心立方(fcc)晶格。在这两种堆积中,空间填充率为74%。剩余的空间以八面体空隙和四面体空隙的形式存在。其他堆积形式不是密堆积,粒子的填充效率较低。在体心立方晶格(bcc)中,空间填充率为68%,而在简单立方晶格中,只有52.4%的空间被填充。 固体的结构并不完美,存在不同类型的缺陷或不完全性。常见的缺陷包括点缺陷和线缺陷。点缺陷有三种类型:化学计量缺陷、杂质缺陷和非化学计量缺陷。在离子固体中,点缺陷表现为弗伦克尔缺陷和肖特基缺陷。杂质缺陷是由于晶体中出现杂质造成的。在离子固体中,当离子杂质的价态与主化合物不同,会产生一些空位。非化学计量缺陷则分为金属过剩型和金属缺乏型。 在半导体中,有时通过掺杂引入计算出的杂质量,以改变其电性质,这些材料广泛用于电子产业。固体显示出多种磁性,如顺磁性、抗磁性、铁磁性、反铁磁性和纤维磁性,这些性质在音频、视频及其他录音设备中有应用。所有这些性质都可以与它们的电子构型或结构相关联。
SUMMARYSolids have definite mass, volume and shape. This is due to the fixed position of their constituent particles, short distances and strong interactions between them. In amorphous solids, the arrangement of constituent particles has only short range order and consequently they behave like super cooled liquids, do not have sharp melting points and are isotropic in nature. In crystalline solids there is long range order in the arrangement of their constituent particles. They have sharp melting points, are anisotropic in nature and their particles have characteristic shapes. Properties of crystalline solids depend upon the nature of interactions between their constituent particles. On this basis, they can be divided into four categories, namely: molecular, ionic, metallic and covalent solids. They differ widely in their properties.The constituent particles in crystalline solids are arranged in a regular pattern which extends throughout the crystal. This arrangement is often depicted in the form of a three dimensional array of points which is called crystal lattice. Each lattice point gives the location of one particle in space. In all, fourteen different types of lattices are possible which are called Bravais lattices. Each lattice can be generated by repeating its small characteristic portion called unit cell. A unit cell is characterised by its edge lengths and three angles between these edges. Unit cells can be either primitive which have particles only at their corner positions or centred. The centred unit cells have additional particles at their body centre (bodycentred), at the centre of each face (face-centred) or at the centre of two opposite faces (end-centred). There are seven types of primitive unit cells. Taking centred unit cells also into account, there are fourteen types of unit cells in all, which result in fourteen Bravais lattices.Close-packing of particles result in two highly efficient lattices, hexagonal close-packed (hcp) and cubic close-packed (ccp). The latter is also called facecentred cubic (fcc) lattice. In both of these packings 74% space is filled. The remaining space is present in the form of two types of voids-octahedral voids and tetrahedral voids. Other types of packing are not close-packings and have less efficient packing of particles. While in body-centred cubic lattice (bcc) 68% space is filled, in simple cubic lattice only 52.4 % space is filled.Solids are not perfect in structure. There are different types of imperfections or defects in them. Point defects and line defects are common types of defects. Point defects are of three types - stoichiometric defects, impurity defects and non-stoichiometric defects. Vacancy defects and interstitial defects are the two basic types of stoichiometric point defects. In ionic solids, these defects are present as Frenkel and Schottky defects. Impurity defects are caused by the presence of an impurity in the crystal. In ionic solids, when the ionic impurity has a different valence than the main compound, some vacancies are created. Nonstoichiometric defects are of metal excess type and metal deficient type. Sometimes calculated amounts of impurities are introduced by doping in semiconductors that change their electrical properties. Such materials are widely used in electronics industry. Solids show many types of magnetic properties like paramagnetism, diamagnetism, ferromagnetism, antiferromagnetism and ferrimagnetism. These properties are used in audio, video and other recording devices. All these properties can be correlated with their electronic configurations or structures.