Electron wave properties

Small metal clusters are also of interest because of their importance in catalysis. Despite the fact that small clusters should consist of mostly surface atoms, measurement of the photon ionization threshold for Hg clusters suggest that a transition from van der Waals to metallic properties occurs in the range of 20-70 atoms per cluster [88] and near-bulk magnetic properties are expected for Ni, Pd, and Pt clusters of only 13 atoms [89] Theoretical calculations on Sin and other semiconductors predict that the stmcture reflects the bulk lattice for 1000 atoms but the bulk electronic wave functions are not obtained [90]. Bartell and co-workers [91] study beams of molecular clusters with electron dirfraction and molecular dynamics simulations and find new phases not observed in the bulk. Bulk models appear to be valid for their clusters of several thousand atoms (see Section IX-3). 

U(qJ is referred to as an adiabatic-to-diabatic transformation (ADT) matrix. Its mathematical sbucture is discussed in detail in Section in.C. If the electronic wave functions in the adiabatic and diabatic representations are chosen to be real, as is normally the case, U(q ) is orthogonal and therefore has n n — l)/2 independent elements (or degrees of freedom). This transformation mabix U(qO can be chosen so as to yield a diabatic electronic basis set with desired properties, which can then be used to derive the diabatic nuclear motion Schrodinger equation. By using Eqs. (27) and (28) and the orthonormality of the diabatic and adiabatic electronic basis sets, we can relate the adiabatic and diabatic nuclear wave functions through the same n-dimensional unitary transformation matrix U(qx) according to... 

Although the leading term of the electronic wave function of the system is thus changed, the total wave function has not and the calculated trajectory and properties exhibit no discontinuous behavior. 

Let us examine a special but more practical case where the total molecular Hamiltonian, H, can be separated to an electronic part, W,.(r,s Ro), as is the case in the usual BO approximation. Consequendy, the total molecular wave function fl(R, i,r,s) is given by the product of a nuclear wave function X uc(R, i) and an electronic wave function v / (r, s Ro). We may then talk separately about the permutational properties of the subsystem consisting of electrons, and the subsystemfs) formed of identical nuclei. Thus, the following commutative laws Pe,Hg =0 and =0 must be satisfied X =... 

In this section, we extend the above discussion to the isotopomers of X3 systems, where X stands for an alkali metal atom. For the lowest two electronic states, the permutational properties of the electronic wave functions are similar to those of Lij. Their potential energy surfaces show that the baniers for pseudorotation are very low [80], and we must regard the concerned particles as identical. The Na atom has a nuclear spin " K, and K have nuclear... 

Valence bond and molecular orbital theory both incorporate the wave description of an atom s electrons into this picture of H2 but m somewhat different ways Both assume that electron waves behave like more familiar waves such as sound and light waves One important property of waves is called interference m physics Constructive interference occurs when two waves combine so as to reinforce each other (m phase) destructive interference occurs when they oppose each other (out of phase) (Figure 2 2) Recall from Section 1 1 that electron waves m atoms are characterized by their wave function which is the same as an orbital For an electron m the most stable state of a hydrogen atom for example this state is defined by the Is wave function and is often called the Is orbital The valence bond model bases the connection between two atoms on the overlap between half filled orbifals of fhe fwo afoms The molecular orbital model assembles a sef of molecular orbifals by combining fhe afomic orbifals of all of fhe atoms m fhe molecule... 

For atoms, electronic states may be classified and selection rules specified entirely by use of the quantum numbers L, S and J. In diatomic molecules the quantum numbers A, S and Q are not quite sufficient. We must also use one (for heteronuclear) or two (for homonuclear) symmetry properties of the electronic wave function ij/. ... 

In the case of atoms (Section 7.1) a sufficient number of quantum numbers is available for us to be able to express electronic selection rules entirely in terms of these quantum numbers. For diatomic molecules (Section 7.2.3) we require, in addition to the quantum numbers available, one or, for homonuclear diatomics, two symmetry properties (-F, — and g, u) of the electronic wave function to obtain selection rules. 

For the orbital parts of the electronic wave functions of two electronic states the selection rules depend entirely on symmetry properties. [In fact, the electronic selection rules can also be obtained, from symmetry arguments only, for diatomic molecules and atoms, using the (or and Kf point groups, respectively but it is more... 

Basically, Newtonian mechanics worked well for problems involving terrestrial and even celestial bodies, providing rational and quantifiable relationships between mass, velocity, acceleration, and force. However, in the realm of optics and electricity, numerous observations seemed to defy Newtonian laws. Phenomena such as diffraction and interference could only be explained if light had both particle and wave properties. Indeed, particles such as electrons and x-rays appeared to have both discrete energy states and momentum, properties similar to those of light. None of the classical, or Newtonian, laws could account for such behavior, and such inadequacies led scientists to search for new concepts in the consideration of the nature of reahty. 

In 1913 Niels Bohr proposed a system of rules that defined a specific set of discrete orbits for the electrons of an atom with a given atomic number. These rules required the electrons to exist only in these orbits, so that they did not radiate energy continuously as in classical electromagnetism. This model was extended first by Sommerfeld and then by Goudsmit and Uhlenbeck. In 1925 Heisenberg, and in 1926 Schrn dinger, proposed a matrix or wave mechanics theory that has developed into quantum mechanics, in which all of these properties are included. In this theory the state of the electron is described by a wave function from which the electron s properties can be deduced. 

Semi-empirical models provide a method for calculating the electronic wave function, which may be used for predicting a variety of properties. There is nothing to hinder the... 

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. 

Here, the orbital phase theory sheds new light on the regioselectivities of reactions [29]. This suggests how widely or deeply important the role of the wave property of electrons in molecules is in chemistry. 

Molecular properties and reactions are controlled by electrons in the molecules. Electrons had been thonght to be particles. Quantum mechanics showed that electrons have properties not only as particles but also as waves. A chemical theory is required to think abont the wave properties of electrons in molecules. These properties are well represented by orbitals, which contain the amplitude and phase characteristics of waves. This volume is a result of our attempt to establish a theory of chemistry in terms of orbitals — A Chemical Orbital Theory. 

We are used to thinking of electrons as particles. As it turns out, electrons display both particle properties and wave properties. The French physicist Louis de Broglie first suggested that electrons display wave-particle duality like that exhibited by photons. De Broglie reasoned from nature s tendency toward symmetry If things that behave like waves (light) have particle characteristics, then things that behave like particles (electrons) should also have wave characteristics. 

The de Broglie equation predicts that eveiy particle has wave characteristics. The wave properties of subatomic particles such as electrons and neutrons play important roles in their behavior, but larger particles such as Ping-Pong balls or automobiles do not behave like waves. The reason is the scale of the waves. For all except subatomic particles, the wavelengths involved are so short that we are unable to detect the wave properties. Example illustrates this. 

A particle occupies a particular location, but a wave has no exact position. A wave extends over some region of space. Because of their wave properties, electrons are always spread out rather than located in one particular place. As a result, the position of a moving electron cannot be precisely defined. We describe electrons as delocalized because their waves are spread out rather than pinpointed. 

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