Electrons wave nature

Crommie M F, Lutz C P and Eigler D M 1993 Imaging standing waves in a two-dimensional electron gas Nature 363 524... 

Until now we have implicitly assumed that our problem is formulated in a space-fixed coordinate system. However, electronic wave functions are naturally expressed in the system bound to the molecule otherwise they generally also depend on the rotational coordinate 4>. (This is not the case for E electronic states, for which the wave functions are invariant with respect to (j> ) The eigenfunctions of the electronic Hamiltonian, v / and v , computed in the framework of the BO approximation ( adiabatic electronic wave functions) for two electronic states into which a spatially degenerate state of linear molecule splits upon bending. 

Since the form of the electronic wave functions depends also on the coordinate p (in the usual, parametric way), the matrix elements (21) are functions of it too. Thus it looks at first sight as if a lot of cumbersome computations of derivatives of the electronic wave functions have to be carried out. In this case, however, nature was merciful the matrix elements in (21) enter the Hamiltonian matrix weighted with the rotational constant A, which tends to infinity when the molecule reaches linear geometry. This means that only the form of the wave functions, that is, of the matrix elements in (21), in the p 0 limit are really needed. In the above mentioned one-elecbon approximation... 

As pointed out in the previous paragraph, the total wave function of a molecule consists of an electronic and a nuclear parts. The electrons have a different intrinsic nature from nuclei, and hence can be treated separately when one considers the issue of permutational symmetry. First, let us consider the case of electrons. These are fermions with spin and hence the subsystem of electrons obeys the Fermi-Dirac statistics the total electronic wave function... 

The Schrodinger equation cannot be subjected to firm proof but was put forward as a postulate, based on the analogy between the wave nature of light and of the electron. The equation was justified by the remarkable successes of its applications. 

When Davisson and Germer reported in 1927 that the elastic scattering of low-energy electrons from well ordered surfaces leads to diffraction spots similar to those observed in X-ray diffraction [2.238-2.240], this was the first experimental proof of the wave nature of electrons. A few years before, in 1923, De Broglie had postulated that electrons have a wavelength, given in A, of ... 

L. V. de Broglie (Paris) discovery of the wave nature of electrons. 

The properties of electrons described so far (mass, charge, spin, and wave nature) apply to all electrons. Electrons traveling freely in space, electrons moving in a copper wire, and electrons bound to atoms all have these characteristics. Bound electrons, those held in a specific region in space by electrical forces, have additional important properties relating to their energies and the shapes of their waves. These additional properties can have only certain specific values, so they are said to be quantized. 

Contrary to fraras-azoferrocene, the cis form exhibits one-step 2e oxidation waves, and its oxidation potential, E° = 0.03 V in Bu4NC104-benzonitrile, is more negative than that of the trans form (E() = 0.29 and 0.50 V vs. Ag/Ag ) by 0.3 V. These data imply that the 7r-conjugation ability and electron-withdrawing nature of the azo group is retarded in the cis form. 

There was no experimental evidence for the wave nature of matter until 1927, when evidence was provided by two independent experiments. Davisson found that a diffraction pattern was obtained if electrons were scattered from a nickel surface, and Thomson found that when a beam of electrons is passed through a thin gold foil, the diffraction pattern obtained is very similar to that produced by a beam of X-rays when it passes through a metal foil. 

In classical mechanics both the position of a particle and its velocity at any given instant can be determined with as much accuracy as the experimental procedure allows. However, in 1927 Heisenberg introduced the idea that the wave nature of matter sets limits to the accuracy with which these properties can be measured simultaneously for a very small particle such as an electron. He showed that Ax, the product of the uncertainty in the measurement of the position x, and Ap, the uncertainty in the measurement of the momentum p, can never be smaller than M2tt ... 

Schrodinger equation valence electrons wave function wavelength, X wave mechanical model wave-particle duality of nature... 

An important difference between the BO and non-BO internal Hamiltonians is that the former describes only the motion of electrons in the stationary field of nuclei positioned in fixed points in space (represented by point charges) while the latter describes the coupled motion of both nuclei and electrons. In the conventional molecular BO calculations, one typically uses atom-centered basis functions (in most calculations one-electron atomic orbitals) to expand the electronic wave function. The fermionic nature of the electrons dictates that such a function has to be antisymmetric with respect to the permutation of the labels of the electrons. In some high-precision BO calculations the wave function is expanded in terms of basis functions that explicitly depend on the interelectronic distances (so-called explicitly correlated functions). Such... 

A small problem arises when the crystal thickness and temperature factors are refined simultaneously, because these parameters are highly correlated. Raising both the thickness and the temperature factors results in almost the same least-squares sum. This is not an artifact of the calculation method but lies in the behavior of nature. Increasing the Debye-Waller factor of an atom means a less peaked scattering potential, which in turn results in a less sharply peaked interaction with the ncident electron wave. It can be shown that a thickness of 5 nm anc B=2 will give about the same results as a thickness of 10 nm and B=6 A. ... 

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