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本课程“物理化学 - 原子结构”深入探讨了构成物质基本单元——原子的结构演变。课程从约翰·道尔顿的早期原子理论出发,介绍了原子并非不可分割的粒子,而是由电子、质子和中子组成的。 随后,课程详细解析了几个重要的原子模型: * **汤姆孙模型(1898年)**:将原子描述为带有嵌入电子的均匀正电荷球体。 * **卢瑟福模型(1909年)**:基于α粒子散射实验,提出原子中心存在一个微小的带正电的原子核,电子围绕原子核运动。尽管此模型改进了汤姆孙模型,但未能解释原子稳定性及电子能级。 * **玻尔模型(1913年)**:成功解释了氢原子光谱,提出了电子在特定轨道上运动且具有特定能量的观点。然而,该模型在解释多电子原子光谱以及处理电子的波粒二象性和海森堡不确定性原理方面存在局限。 课程的重点转向了量子力学模型: * **薛定谔方程(1926年)**:引入了描述电子分布的空间和原子中允许的能量水平的薛定谔方程。该方程结合了德布罗意的波粒二象性概念,并与海森堡不确定性原理相符。 * **量子力学原子模型**:通过求解薛定谔方程(以氢原子为例),引出了电子的能量状态和对应的波函数,这些状态由三个量子数(主量子数n、角量子数l和磁量子数ml)描述。 * **电子壳层、亚层和轨道**:课程阐述了电子在原子中的分布结构,即由壳层、亚层和轨道组成。 * **多电子原子的能量规则**:解释了多电子原子中轨道的能量顺序,基于(n+l)值和n值。 * **电子填充原理**:根据泡利不相容原理和洪特规则,详细说明了电子如何填充这些轨道,从而构成了原子的电子结构基础。 总之,本课程系统地梳理了原子结构认识的历史进程,最终聚焦于量子力学模型,为理解化学反应和物质性质奠定了基础。
SUMMARYAtoms are the building blocks of elements. They are the smallest parts of an element that chemically react. The first atomic theory, proposed by John Dalton in 1808, regarded atom as the ultimate indivisible particle of matter. Towards the end of the nineteenth century, it was proved experimentally that atoms are divisible and consist of three fundamental particles: electrons, protons and neutrons. The discovery of sub-atomic particles led to the proposal of various atomic models to explain the structure of atom.Thomson in 1898 proposed that an atom consists of uniform sphere of positive electricity with electrons embedded into it. This model in which mass of the atom is considered to be evenly spread over the atom was proved wrong by Rutherford's famous alpha-particle scattering experiment in 1909. Rutherford concluded that atom is made of a tiny positively charged nucleus, at its centre with electrons revolving around it in circular orbits. Rutherford model, which resembles the solar system, was no doubt an improvement over Thomson model but it could not account for the stability of the atom i.e., why the electron does not fall into the nucleus. Further, it was also silent about the electronic structure of atoms i.e., about the distribution and relative energies of electrons around the nucleus. The difficulties of the Rutherford model were overcome by Niels Bohr in 1913 in his model of the hydrogen atom. Bohr postulated that electron moves around the nucleus in circular orbits. Only certain orbits can exist and each orbit corresponds to a specific energy. Bohr calculated the energy of electron in various orbits and for each orbit predicted the distance between the electron and nucleus. Bohr model, though offering a satisfactory model for explaining the spectra of the hydrogen atom, could not explain the spectra of multi-electron atoms. The reason for this was soon discovered. In Bohr model, an electron is regarded as a charged particle moving in a well defined circular orbit about the nucleus. The wave character of the electron is ignored in Bohr's theory. An orbit is a clearly defined path and this path can completely be defined only if both the exact position and the exact velocity of the electron at the same time are known. This is not possible according to the Heisenberg uncertainty principle. Bohr model of the hydrogen atom, therefore, not only ignores the dual behaviour of electron but also contradicts Heisenberg uncertainty principle.Erwin Schrödinger, in 1926, proposed an equation called Schrödinger equation to describe the electron distributions in space and the allowed energy levels in atoms. This equation incorporates de Broglie's concept of wave-particle duality and is consistent with Heisenberg uncertainty principle. When Schrödinger equation is solved for the electron in a hydrogen atom, the solution gives the possible energy states the electron can occupy [and the corresponding wave function(s) (ψ) (which in fact are the mathematical functions) of the electron associated with each energy state]. These quantized energy states and corresponding wave functions which are characterized by a set of three quantum numbers (principal quantum number n, azimuthal quantum number l and magnetic quantum number ml ) arise as a natural consequence in the solution of the Schrödinger equation. The restrictions on the values of these three quantum numbers also come naturally from this solution. The quantum mechanical model of the hydrogen atom successfully predicts all aspects of the hydrogen atom spectrum including some phenomena that could not be explained by the Bohr model.According to the quantum mechanical model of the atom, the electron distribution of an atom containing a number of electrons is divided into shells. The shells, in turn, are thought to consist of one or more subshells and subshells are assumed to be composed of one or more orbitals, which the electrons occupy. While for hydrogen and hydrogen like systems (such as He+ , Li2+ etc.) all the orbitals within a given shell have same energy, the energy of the orbitals in a multi-electron atom depends upon the values of n and l: The lower the value of (n + l ) for an orbital, the lower is its energy. If two orbitals have the same (n + l ) value, the orbital with lower value of n has the lower energy. In an atom many such orbitals are possible and electrons are filled in those orbitals in order of increasing energy in accordance with Pauli exclusion principle (no two electrons in an atom can have the same set of four quantum numbers) and Hund's rule of maximum multiplicity (pairing of electrons in the orbitals belonging to the same subshell does not take place until each orbital belonging to that subshell has got one electron each, i.e., is singly occupied). This forms the basis of the electronic structure of atoms.