The second model is a quantum mechanical one where free electrons are contained in a box whose sides correspond to the surfaces of the metal. The wave functions for the standing waves inside the box yield permissible states essentially independent of the lattice type. The kinetic energy corresponding to the rejected states leads to the surface energy in fair agreement with experimental estimates [86, 87],... [Pg.270]

A number of procedures have been proposed to map a wave function onto a function that has the form of a phase-space distribution. Of these, the oldest and best known is the Wigner function [137,138]. (See [139] for an exposition using Louiville space.) For a review of this, and other distributions, see [140]. The quantum mechanical density matrix is a matrix representation of the density operator... [Pg.270]

The big advantage of the Gaussian wavepacket method over the swarm of trajectory approach is that a wave function is being used, which can be easily manipulated to obtain quantum mechanical information such as the spechum, or reaction cross-sections. The initial Gaussian wave packet is chosen so that it... [Pg.273]

Both the BO dynamics and Gaussian wavepacket methods described above in Section n separate the nuclear and electronic motion at the outset, and use the concept of potential energy surfaces. In what is generally known as the Ehrenfest dynamics method, the picture is still of semiclassical nuclei and quantum mechanical electrons, but in a fundamentally different approach the electronic wave function is propagated at the same time as the pseudoparticles. These are driven by standard classical equations of motion, with the force provided by an instantaneous potential energy function... [Pg.290]

The concept of two-state systems occupies a central role in quantum mechanics [16,26]. As discussed extensively by Feynmann et al. [16], benzene and ammonia are examples of simple two-state systems Their properties are best described by assuming that the wave function that represents them is a combination of two base states. In the cases of ammonia and benzene, the two base states are equivalent. The two base states necessarily give rise to two independent states, which we named twin states [27,28]. One of them is the ground state, the other an excited states. The twin states are the ones observed experimentally. [Pg.330]

At this point, it is instructive to discuss the distinction between molecules, anchors, and quantum mechanical wave functions that represent them. The topic is best introduced by using an example. Consider the H4 system [34]. [Pg.333]

Because of the quantum mechanical Uncertainty Principle, quantum m echanics methods treat electrons as indistinguishable particles, This leads to the Paiili Exclusion Pnn ciple, 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. [Pg.34]

A central multipole expansion therefore provides a way to calculate the electrostatic interaction between two molecules. The multipole moments can be obtained from the wave-function and can therefore be calculated using quantum mechanics (see Section 2.7.3) or can be determined from experiment. One example of the use of a multipole expansion is... [Pg.203]

The fact that an electron has an intrinsic spin comes out of a relativistic formulation of quantum mechanics. Even though the Schrodinger equation does not predict it, wave functions that are antisymmetric and have two electrons per orbital are used for nonreiativistic calculations. This is necessary in order to obtain results that are in any way reasonable. [Pg.261]

HyperChem can plot orbital wave functions resulting from semi-empirical and ab initio quantum mechanical calculations. It is interesting to view both the nodal properties and the relative sizes of the wave functions. Orbital wave functions can provide chemical insights. [Pg.9]

Both molecular and quantum mechanics methods rely on the Born-Oppenheimer approximation. In quantum mechanics, the Schrodinger equation (1) gives the wave functions and energies of a molecule. [Pg.11]

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. [Pg.35]

Quantum mechanics calculations use either of two forms of the wave function Restricted Hartree-Fock (RHF) or Unrestricted Hartree-Fock (UHF). Use the RHF wave function for singlet electronic states, such as the ground states of stable organic molecules. [Pg.37]

In the quantum mechanical description of dipole moment, the charge is a continuous distribution that is a function of r, and the dipole moment is an average over the wave function of the dipole moment operator, p ... [Pg.52]

The setup of these calculations is very similar for both quantum and molecular mechanics. In practice, molecular dynamics calculation s using the nl) initio and semi-empirical quantum mechanical SCFmethods are limited to relatively small systems. Each time step requires a complete calculation of the wave function and the forces. [Pg.121]

For a quantum mechanical calculation, the single point calculation leads to a wave function for the molecular system and considerably more information than just the energy and gradient are available. In principle, any expectation value might be computed. You can get plots of the individual orbitals, the total (or spin) electron density and the electrostatic field around the molecule. You can see the orbital energies in the status line when you plot an orbital. Finally, the log file contains additional information including the dipole moment of the molecule. The level of detail may be controlled by the PrintLevel entry in the chem.ini file. [Pg.301]

For the quantum mechanical results that we require we shall be concerned only with stationary states, known sometimes as eigenstates. The wave functions for these states may be referred to as eigenfunctions and the associated energies E as the eigenvalues. [Pg.11]

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