Hydrogen Schrodinger

The canonical real d-orbital wave functions are linear combinations of the complex eigen functions (solutions) of the hydrogenic Schrodinger equation and the orbital angular momentum operator. Thus, instead of a set of five degenerate orbitals that may be indexed by values of orbital... 

Although it is typically solved in spherical and parabolic coordinates, the hydrogenic Schrodinger equation is also separable in prolate spheroidal coordinates, with one focus at the nucleus and the other located along the Lenz vector at a distance R away. These coordinates are ordinarily used for two- center problems such as H. Previously, general features of the spheroidal hydrogen atom have been explored by Coulson and Robinson [6], who noted that the limits R —> 0 and R —> oo yield the spherical and parabolic solutions, respectively. Demkov [7] used the spheroidal eigenfunctions to construct... 

Therefore, the working Hydrogenic Schrodinger radial equation has the form... 

The miderstanding of the quantum mechanics of atoms was pioneered by Bohr, in his theory of the hydrogen atom. This combined the classical ideas on planetary motion—applicable to the atom because of the fomial similarity of tlie gravitational potential to tlie Coulomb potential between an electron and nucleus—with the quantum ideas that had recently been introduced by Planck and Einstein. This led eventually to the fomial theory of quaiitum mechanics, first discovered by Heisenberg, and most conveniently expressed by Schrodinger in the wave equation that bears his name. 

I 1 11 Schrodinger equation can be solved exactly for only a few problems, such as the particle in a box, the harmonic oscillator, the particle on a ring, the particle on a sphere and the hydrogen atom, all of which are dealt with in introductory textbooks. A common feature of these problems is that it is necessary to impose certain requirements (often called boundary... 

The Hydrogenic atom problem forms the basis of much of our thinking about atomic structure. To solve the corresponding Schrodinger equation requires separation of the r, 0, and (j) variables... 

For both types of orbitals, the coordinates r, 0, and (j) refer to the position of the electron relative to a set of axes attached to the center on which the basis orbital is located. Although Slater-type orbitals (STOs) are preferred on fundamental grounds (e.g., as demonstrated in Appendices A and B, the hydrogen atom orbitals are of this form and the exact solution of the many-electron Schrodinger equation can be shown to be of this form (in each of its coordinates) near the nuclear centers), STOs are used primarily for atomic and linear-molecule calculations because the multi-center integrals < XaXbl g I XcXd > (each... 

These atomic orbitals, called Slater Type Orbitals (STOs), are a simplification of exact solutions of the Schrodinger equation for the hydrogen atom (or any one-electron atom, such as Li" ). Hyper-Chem uses Slater atomic orbitals to construct semi-empirical molecular orbitals. The complete set of Slater atomic orbitals is called the basis set. Core orbitals are assumed to be chemically inactive and are not treated explicitly. Core orbitals and the atomic nucleus form the atomic core. 

As I mentioned above, it is conventional in many engineering applications to seek to rewrite basic equations in dimensionless form. This also applies in quantum-mechanical applications. For example, consider the time-independent electronic Schrodinger equation for a hydrogen atom... 

So, let s get a bit more chemical and imagine the formation of an H2 molecule from two separated hydrogen atoms, Ha and Hb, initially an infinite distance apart. Electron 1 is associated with nucleus A, electron 2 with nucleus B, and the terms in the electronic Hamiltonian / ab, ba2 and are all negligible when the nuclei are at infinite separation. Thus the electronic Schrodinger equation becomes... 

Exact solutions to the electronic Schrodinger equation are not possible for many-electron atoms, but atomic HF calculations have been done both numerically and within the LCAO model. In approximate work, and for molecular applications, it is desirable to use basis functions that are simple in form. A polyelectron atom is quite different from a one-electron atom because of the phenomenon of shielding", for a particular electron, the other electrons partially screen the effect of the positively charged nucleus. Both Zener (1930) and Slater (1930) used very simple hydrogen-like orbitals of the form... 

The Bom-Oppenheimer approximation is usually very good. For the hydrogen molecule the error is of the order of 10 ", and for systems with heavier nuclei, the approximation becomes better. As we shall see later, it is only possible in a few cases to solve the electronic part of the Schrodinger equation to an accuracy of 10 ", i.e. neglect of the nuclear-electron coupling is usually only a minor approximation compared with other errors. 

Some coordinate transformations are non-linear, like transforming Cartesian to polar coordinates, where the polar coordinates are given in terms of square root and trigonometric functions of the Cartesian coordinates. This for example allows the Schrodinger equation for the hydrogen atom to be solved. Other transformations are linear, i.e. the new coordinate axes are linear combinations of the old coordinates. Such transfonnations can be used for reducing a matrix representation of an operator to a diagonal form. In the new coordinate system, the many-dimensional operator can be written as a sum of one-dimensional operators. 

In 1926 Erwin Schrodinger (1887-1961), an Austrian physicist, made a major contribution to quantum mechanics. He wrote down a rather complex differential equation to express the wave properties of an electron in an atom. This equation can be solved, at least in principle, to find the amplitude (height) of the electron wave at various points in space. The quantity ip (psi) is known as the wave function. Although we will not use the Schrodinger wave equation in any calculations, you should realize that much of our discussion of electronic structure is based on solutions to that equation for the electron in the hydrogen atom. 

The quantum number ms was introduced to make theory consistent with experiment. In that sense, it differs from the first three quantum numbers, which came from the solution to the Schrodinger wave equation for the hydrogen atom. This quantum number is not related to n, , or mi. It can have either of two possible values ... 

I restrict my attention to non-relativistic pioneer quantum mechanics of 1925-6, and even further to the time independent formulation. Numerous other developments have taken place in quantum theory, such as Dirac s relativistic treatment of the hydrogen atom (Dirac [1928]) and various modern quantum field theories have been constructed (Redhead [1986]). Also, much work has been done in the philosophy of quantum theory such as the question of E.P.R. correlations (Bell [1966]). However, it seems fair to say that no fundamental change has occurred in quantum mechanics since the pioneer version was established. The version of quantum mechanics used on a day-to-day basis by most chemists and physicists remains as the 1925-6 version (Heisenberg [1925], Schrodinger [1926]). 

Suppose we get a little more sophisticated about our question. The more advanced student might respond that the periodic table can be explained in terms of the relationship between the quantum numbers which themselves emerge from the solutions to the Schrodinger equation for the hydrogen atom.5... 

As many textbooks correctly report, the number of electrons that can be accommodated into any electron shell coincides with the range of values for the three quantum numbers that characterize the solutions to the Schrodinger equation for the hydrogen atom and the fourth quantum number as first postulated by Pauli. 

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