Nuclear point-like nuclei

For both the top slice model (T) and the homogeneous model (H), the potential is represented exactly by the Coulomb potential of a pointlike nucleus, —Z/r, beyond their respective nuclear size parameter. This function is approached only asymptotically by the potentials obtained from the Gaussian and Fermi-type models (G and F). In practice, however, the absolute deviation of these latter potentials from the Coulomb potential of the point-like nucleus is lower than machine precision (double precision) beyond a radius of about ten times the rms radius at most. 

In this last section we mention a few cases, where properties other than the energy of a system are considered, which are influenced in particular by the change from the point-like nucleus case (PNC) to the finite nucleus case (FNC) for the nuclear model. Firstly, we consider the electron-nuclear contact term (Darwin term), and turn then to higher quantum electrodynamic effects. In both cases the nuclear charge density distribution p r) is involved. The next item, parity non-conservation due to neutral weak interaction between electrons and nuclei, involves the nuclear proton and neutron density distributions, i.e., the particle density ditributions n r) and n (r). Finally, higher nuclear electric multipole moments, which involve the charge density distribution p r) again, are mentioned briefly. 

The Poisson equation for the nuclear potential V in the case of the point-like nucleus reads ... 

We have already seen above that the choice of a point-like atomic nucleus limits the Dirac theory to atoms with a nuclear charge number Z < c, i.e., Zmax 137. A nonsingular electron-nucleus potential energy operator allows us to overcome this limit if an atomic nucleus of finite size is used. In relativistic electronic structure calculations on atoms — and thus also for calculations on molecules — it turned out that the effect of different finite-nucleus models on the total energy is comparable but distinct from the energy of a point-like nucleus (compare also section 9.8.4). 

Figure 6.6 Comparison of ground-state energies E[glZ scaled by I7 obtained tor hydrogen-iike atoms from Schrodinger quantum mechanics (horizontal line on top at -0.5 hartree), from Dirac theory with a Couiomb potential from a point-like nucleus (dashed line) and from Dirac theory with a finite nuclear charge distribution of Gaussian form (thin black line). The highest energy of the positronic continuum states, -2meC, appears as a thick black line, which is bent because of the l/Z scaling.

We only briefly mention that a similar modification, i.e., a change from a Dirac delta distribution to an extended distribution, would be required for the spin-dependent electron-nucleus contact term, known as Fermi contact term, if the usual point-like nuclear magnetization distribution (the pointlike nuclear magnetic dipole approximation) is replaced by an extended nuclear magnetization distribution. 

Finally, in Sect. 6, we have briefly given some examples for physical properties or effects, which involve the nuclear charge density distribution or the nucleon distribution in a more direct way, such that the change from a point-like to an extended nucleus is not unimportant. These include the electron-nucleus Darwin term, QED effects like vacuum polarization, and parity non-conservation due to neutral weak interaction. Hyperfine interaction, i.e., the interaction between higher nuclear electric (and magnetic)... 

All science is based on a number of axioms (postulates). Quantum mechanics is based on a system of axioms that have been formulated to be as simple as possible and yet reproduce experimental results. Axioms are not supposed to be proved, their justification is efficiency. Quantum mechanics, the foundations of which date from 1925-26, still represents the basic theory of phenomena within atoms and molecules. This is the domain of chemistry, biochemistry, and atomic and nuclear physics. Further progress (quantum electrodynamics, quantum field theory, elementary particle theory) permitted deeper insights into the structure of the atomic nucleus, but did not produce any fundamental revision of our understanding of atoms and molecules. Matter as described at a non-relativistic quantum mechanics represents a system of electrons and nuclei, treated as point-like particles with a definite mass and electric charge, moving in three-dimensional space and interacting by electrostatic forces. This model of matter is at the core of quantum chemistry. Fig. 1.2. 

Once the nuclear coordinates are expressed in the inertial reference frame, one can locate the extreme points occupied by a nucleus in the molecule along each of the three inertial axes, thus defining three limiting molecular dimensions (Table 1.1 and Fig. 1.1). The radii of the peripheral atoms (see below) may be added to these dimensions. The axis corresponding to the highest moment is perpendicular to the plane of maximum spread of nuclear positions - like, for example, the molecular... 

However, the nuclear spins are envisioned as point-like spectators of the surrounding electron clouds, with each nucleus signahng its unique chemical bonding environment through a pronounced resonance frequency shift, whereas the electron spins are spatially dispersed over multiple nuclei and exhibit only subtle shifts in resonance frequency. The ESR signals reflect the much more active participation of electron spins in the chemical interactions under study. 

The discussion thus far has focused on the forces between an array of atoms connected together through covalent bonds and their angles. Important interactions occur between atoms not directly bonded together. The theoretical explanation for attractive and repulsive forces for nonbonded atoms i and j is based on electron distributions. The motion of electrons about a nucleus creates instantaneous dipoles. The instantaneous dipoles on atom i induce dipoles of opposite polarity on atom j. The interactions between the instantaneous dipole on atom i with the induced instantaneous dipole on atom j of the two electron clouds of nonbonded atoms are responsible for attractive interactions. The attractive interactions are know as London Dispersion forces,70 which are related to r 6, where r is the distance between nonbonded atoms i and j. As the two electron clouds of nonbonded atoms i and j approach one another, they start to overlap. There is a point where electron-electron and nuclear-nuclear repulsion of like charges overwhelms the London Dispersion forces.33 The repulsive... 

This experiment established the nuclear model of the atom. A key point derived from this is that the electrons circling the nucleus are in fixed stable orbits, just like the planets around the sun. Furthermore, each orbital or shell contains a fixed number of electrons additional electrons are added to the next stable orbital above that which is full. This stable orbital model is a departure from classical electromagnetic theory (which predicts unstable orbitals, in which the electrons spiral into the nucleus and are destroyed), and can only be explained by quantum theory. The fixed numbers for each orbital were determined to be two in the first level, eight in the second level, eight in the third level (but extendible to 18) and so on. Using this simple model, chemists derived the systematic structure of the Periodic Table (see Appendix 5), and began to... 

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