Schrodinger equation, electronic

The electronic SE focuses on the energy levels of the molecule. By obtaining the lowest energy, one assumes that the associated wave function will yield the electron distribution of the electronic ground state. An alternative theory has come into recent prominance, in which the SE is bypassed and attention focused on the electron density from which many desired properties including energy can derived directly [density functional theory (DFT)]. 

The most general version of Hartree-Fock (HF) theory, in which each electron is permitted to have its own spin and spatial wave function, is called unrestricted HF (UHF). Remarkably, when a UHF calculation is performed on most molecules which have an equal number of alpha and beta electrons, the spatial parts of the alpha and beta electrons are identical in pairs. Thus the picture that two electrons occupy the same MO with opposite spins comes naturally from this theory. A significant simplification in the solution of the Fock equations ensues if one imposes this natural outcome as a restriction. The form of HF theory where electrons are forced to occupied MOs in pairs is called restricted HF (RHF), and the resulting wave function is of the RHF type. A cal- 

The potential energy F(Q) for a particular electronic state is defined within the Bom-Oppenheimer approximation through the electronic Schrodinger equation (Daudel, Leroy, Peeters, and Sana 1983 ch.7 Lefebvre-Brion and Field 1986 ch.2) 

In general, (1.9) must be solved numerically by quantum chemical or so-called ab initio methods (Lowe 1978 Szabo and Ostlund 1982 Daudel et al. 1983 Dykstra 1988 Hirst 1990 ch.2). The pointwise solution of (1.9) for a set of nuclear geometries and the fitting of all points to an analytical representation yields the PES which is the input to the subsequent dynamics calculations. In principle, one expands Ee (q Q) in a suitable set of electronic basis functions and diagonalizes the corresponding Hamilton matrix, i.e., the representation of Hei within the chosen basis of electronic wavefunctions. Since the number of electrons is usually large, even for simple molecules like H2O and C1NO, the solution of 

We will not discuss the actual construction of potential energy surfaces. This monograph deals exclusively with the nuclear motion taking place on a PES and the relation of the various types of cross sections to particular features of the PES. The investigation of molecular dynamics is — in the context of classical mechanics — equivalent to rolling a billiard ball on a multi-dimensional surface. The way in which the forces i fc(Q) determine the route of the billiard ball is the central topic of this monograph. In the following we discuss briefly two illustrative examples which play key roles in the subsequent chapters. 

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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... 

One of the advantages of this method is that it breaks the many-electron Schrodinger equation into many simpler one-electron equations. Each one-electron equation is solved to yield a single-electron wave function, called an orbital, and an energy, called an orbital energy. The orbital describes the behavior of an electron in the net field of all the other electrons. 

After solving the electronic Schrodinger equation (equation 4), to calculate a potential energy surface, you must add back nuclear-nuclear repulsions (equation 5). 

This last equation is the nuclear Schrodinger equation describing the motion of nuclei. The electronic energy computed from solving the electronic Schrodinger equation (3) on page 163 plus the nuclear-nuclear interactions Vjjjj(R,R) provide a potential for nuclear motion, a Potential Energy Surface (PES). 

Within the Born-Oppenheimer approximation discussed earlier, you can solve an electronic Schrodinger equation... 

Electrons are identical, and each term in this sum is essentially the same operator. You can then solve an independent-electron Schrodinger equation for a wave function /, describing an individual electron ... 

Now that you know the mathematical form, you can solve the independent-electron Schrodinger equation for the molecular orbitals. First substitute the LCAO form above into equation (47) on page 193, multiply on the left by and integrate to represent... 

HyperChem models the vibrations of a molecule as a set of N point masses (the nuclei of the atoms) with each vibrating about its equilibrium (optimized) position. The equilibrium positions are determined by solving the electronic Schrodinger equation. 

This satisfies the electronic Schrodinger equation exactly, giving... 

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... 

The energy s and the distance r are both real physical quantities, with a measure md a unit. If we define the variables r,ed = r/rio and fired = / h, then both id fired are dimensionless. The idea is to rewrite the electronic Schrodinger equation in terms of the dimensionless variables, giving a much simpler dimensionless equation. 

You will see shortly that an exact solution of the electronic Schrodinger equation is impossible, because of the electron-electron repulsion term g(ri, r2). What we have to do is investigate approximate solutions based on chemical intuition, and then refine these models, typically using the variation principle, until we attain the required accuracy. This means in particular that any approximate solution will not satisfy the electronic Schrodinger equation, and we will not be able to calculate the energy from an eigenvalue equation. First of all, let s see why the problem is so difficult. 

We then substitute this wavefunction into the electronic Schrodinger equation, and study the consequences. Do the substitution yourself, divide either side by... 

The orbital model would be exact were the electron repulsion terms negligible or equal to a constant. Even if they were negligible, we would have to solve an electronic Schrodinger equation appropriate to CioHs " " in order to make progress with the solution of the electronic Schrodinger equation for naphthalene. Every molecular problem would be different. 

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 electrons are treated as independent particles constrained to a three-dimensional box, treated here for simplicity as a cube of side L. The box contains the metallic sample. The potential U is infinite outside the box, and a constant Uq inside the box. We focus attention on a single electron whose electronic Schrodinger equation is... 

Once the electronic Schrodinger equation has been solved for a large number of nuclear geometries (and possibly also for several electronic states), the PES is known. This can then be used for solving the nuclear part of the Schrodinger equation. If there are N nuclei, there are 3N coordinates that define the geometry. Of these coordinates, three describe the overall translation of the molecule, and three describe the overall rotation of the molecule with respect to three axes. Eor a linear molecule, only two coordinates are necessary for describing the rotation. This leaves 3N-6(5) coordinates to describe the internal movement of the nuclei, the vibrations, often chosen to be... 

In the Bom-Oppenheimer picture the nuclei move on a potential energy surface (PES) which is a solution to the electronic Schrodinger equation. The PES is independent of the nuclear masses (i.e. it is the same for isotopic molecules), this is not the case when working in the adiabatic approximation since the diagonal correction (and mass polarization) depends on the nuclear masses. Solution of (3.16) for the nuclear wave function leads to energy levels for molecular vibrations (Section 13.1) and rotations, which in turn are the fundamentals for many forms of spectroscopy, such as IR, Raman, microwave etc. 

Having stated the limitations (non-relativistic Hamilton operator and the Bom-Oppenheimer approximation), we are ready to consider the electronic Schrodinger equation. It can only be solved exactly for the Hj molecule, and similar one-electron systems. In the general case we have to rely on approximate (numerical) methods. By neglecting relativistic effects, we also have to introduce electron spin as an ad hoc quantum effect. Each electron has a spin quantum number of 1 /2. In the presence of an... 

There is an equivalent way of generating solutions to the electronic Schrodinger equation which conceptually is much closer to the experimentalists language, known as Valence Bond (VB) theory. We will start by illustrating the concepts for the H2 molecule, and note how it differ from MO methods. 

It would certainly be worth while to study the energy rule from first principles, i.e. on the basis of the many-electron Schrodinger equation, (p.334). 

Given the solutions to the electronic Schrodinger equation, the solutions of the full Schrodinger equation (i.e., the equation in which all nuclei and electrons are moving)... 

The molecular constants o , B, Xe, D, and ae for any diatomic molecule may be determined with great accuracy from an analysis of the molecule s vibrational and rotational spectra." Thus, it is not necessary in practice to solve the electronic Schrodinger equation (10.28b) to obtain the ground-state energy o(R). 

Before we start looking at possible approximations to Exc we need to address whether there will be some kind of guidance along the way. If we consider conventional, wave function based methods for solving the electronic Schrodinger equation, the quality of the... 

Many chemical problems can be discussed by way of a knowledge of the electronic state of molecules. The electronic state of a molecular system becomes known if we solve the electronic Schrodinger equation, which can be separated from the time-independent, nonrelativistic Schrodinger equation for the whole molecule by the use of the Bom-Oppenheimer approximation D. In this approximation, the electrons are considered to move in the field of momentarily fixed nuclei. The nuclear configuration provides the parameters in the Schrodinger equation. 

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