Exclusion principle

Because of the quantum mechanical Uncertainty Principle, quantum mechanics methods treat electrons as indistinguishable particles. This leads to the Pauli Exclusion Principle, which states that the many-electron wave function—which depends on the coordinates of all the electrons—must change sign whenever two electrons interchange positions. That is, the wave function must be antisymmetric with respect to pair-wise permutations of the electron coordinates. 

The Exclusion Principle is fundamentally important in the theory of electronic structure it leads to the picture of electrons occupying distinct molecular orbitals. Molecular orbitals have well-defined energies and their shapes determine the bonding pattern of molecules. Without the Exclusion Principle, all electrons could occupy the same orbital. 

The Exclusion Principle is quantum mechanical in nature, and outside the realm of everyday, classical experience. Think of it as the inherent tendency of electrons to stay away from one another to be mutually excluded. Exclusion is due to the antisymmetry of the wave function and not to electrostatic coulomb repulsion between two electrons. Exclusion exists even in the absence of electrostatic repulsions. 

Consider what happens to the many-electron wave function when two electrons have identical coordinates. Since the electrons have the same coordinates, they are indistinguishable the wave function should be the same if they trade positions. Yet the Exclusion Principle requires that the wave function change sign. Only a zero value for the wave function can satisfy these two conditions, identity of coordinates and an antisymmetric wave function. Eor the hydrogen molecule, the antisymmetric wave function is a(l)b(l)- 

Density Functional Theory (DFT), Hartree-Fock (HF), and the Self-consistent Field. 

Mattis, The Many-Body Problem An Encyclopedia of Exactly Solved Models in One Dimension , Word Scientific, Singapore, 1993. 

Flugge, Practical Quantum Mechanics , Springer-Verlag, New York, 1970. 

Schaefer III, Methods of Electronic Structure Theory , Plenum Press, New York, 1977. 

Parr and W. Yang, Density Functional Theory of Atoms and Molecules , Academic Press, New York, 1989. 

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Pauli exclusion principle In any atom no two electrons can have all four quantum numbers the same. See exclusion principle. 

Since it is not possible to generate antisynnnetric combinations of products if the same spin orbital appears twice in each tenn, it follows that states which assign the same set of four quantum numbers twice cannot possibly satisfy the requirement P.j i = -ij/, so this statement of the exclusion principle is consistent with the more general symmetry requirement. An even more general statement of the exclusion principle, which can be regarded as an additional postulate of quantum mechanics, is... 

The resolution of this issue is based on the application of the Pauli exclusion principle and Femii-Dirac statistics. From the free electron model, the total electronic energy, U, can be written as... 

The state F) is such that the particle states a, b, c,..., q are occupied and each particle is equally likely to be in any one of the particle states. However, if two of the particle states a, b, c,...,q are the same then F) vanishes it does not correspond to an allowed state of the assembly. This is a characteristic of antisynmietric states and it is called the Pauli exclusion principle no two identical fennions can be in the same particle state. The general fimction for an assembly of bosons is... 

The sum over n. can now be perfonned, but this depends on the statistics that the particles in the ideal gas obey. Fenni particles obey the Pauli exclusion principle, which allows only two possible values n. = 0, 1. For Bose particles, n. can be any integer between zero and infinity. Thus the grand partition fiinction is... 

The average kinetic energy per particle at J= 0, is of the Fenni energy p. At constant A, the energy increases as the volume decreases smce fp Due to the Pauli exclusion principle, the Fenni energy gives... 

Themiodynamic stability requires a repulsive core m the interatomic potential of atoms and molecules, which is a manifestation of the Pauli exclusion principle operating at short distances. This means that the Coulomb and dipole interaction potentials between charged and uncharged real atoms or molecules must be supplemented by a hard core or other repulsive interactions. Examples are as follows. 

X molecular spin orbitals must be different from one another in a way that satisfies the Exclusion Principle. Because the wave function IS written as a determinan t. in torch an gin g two rows of Ihe determinant corresponds to interchanging th e coordin ates of Ihe two electrons. The determinant changes sign according to the antisymmetry requirement. It also changes sign when tw O col-uni n s arc in tcrch an ged th is correspon ds to in Lerch an gin g two spin orbitals. 

Because single-electron wave functions are approximate solutions to the Schroe-dinger equation, one would expect that a linear combination of them would be an approximate solution also. For more than a few basis functions, the number of possible lineal combinations can be very large. Fortunately, spin and the Pauli exclusion principle reduce this complexity. 

In addition to being negatively charged electrons possess the property of spin The spin quantum number of an electron can have a value of either +5 or According to the Pauli exclusion principle, two electrons may occupy the same orbital only when... 

Pauli exclusion principle (Section 1 1) No two electrons can have the same set of four quantum numbers An equivalent expression is that only two electrons can occupy the same orbital and then only when they have opposite spins PCC (Section 15 10) Abbreviation for pyndimum chlorochro mate C5H5NH" ClCr03 When used in an anhydrous medium PCC oxidizes pnmary alcohols to aldehydes and secondary alcohols to ketones... 

The simplest many-electron wave function that satisfies the Exclusion Principle is a product of N different one-electron functions that have been antisymmetrized, or written as a determinant. Here, N is the number of electrons (or valence electrons) in the molecule. HyperChem uses this form of the wave function for most semi-empirical and ab initio calculations. Exceptions involve using the Configuration Interaction option (see page 119). HyperChem computes one-electron functions, termed molecular spin orbitals, by relatively simple integration and summation calculations. The many-electron wave function, which has N terms (the number of terms in the determinant), never needs to be evaluated. 

Cl calculations can be used to improve the quality of the wave-function and state energies. Self-consistent field (SCF) level calculations are based on the one-electron model, wherein each electron moves in the average field created by the other n-1 electrons in the molecule. Actually, electrons interact instantaneously and therefore have a natural tendency to avoid each other beyond the requirements of the Exclusion Principle. This correlation results in a lower average interelectronic repulsion and thus a lower state energy. The difference between electronic energies calculated at the SCF level versus the exact nonrelativistic energies is the correlation energy. 

Again, for the filled orbitals L = 0 and 5 = 0, so we have to consider only the 2p electrons. Since n = 2 and f = 1 for both electrons the Pauli exclusion principle is in danger of being violated unless the two electrons have different values of either or m. For non-equivalent electrons we do not have to consider the values of these two quantum numbers because, as either n or f is different for the electrons, there is no danger of violation. 

Intrinsic Semiconductors. For semiconductors in thermal equiHbrium, (Ai( )), the average number of electrons occupying a state with energy E is governed by the Fermi-Dirac distribution. Because, by the Pauli exclusion principle, at most one electron (fermion) can occupy a state, this average number is also the probabiHty, P E), that this state is occupied (see Fig. 2c). In equation 2, K... 

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