Spherical-harmonics method

We have extended the linear combination of Gaussian-type orbitals local-density functional approach to calculate the total energies and electronic structures of helical chain polymers[35]. This method was originally developed for molecular systems[36-40], and extended to two-dimensionally periodic sys-tems[41,42] and chain polymers[34j. The one-electron wavefunctions here are constructed from a linear combination of Bloch functions c>>, which are in turn constructed from a linear combination of nuclear-centered Gaussian-type orbitals Xylr) (in ihis case, products of Gaussians and the real solid spherical harmonics). The one-electron density matrix is given by... 

Here, n corresponds to the principal quantum number, the orbital exponent is termed and Ylm are the usual spherical harmonics that describe the angular part of the function. In fact as a rule of thumb one usually needs about three times as many GTO than STO functions to achieve a certain accuracy. Unfortunately, many-center integrals such as described in equations (7-16) and (7-18) are notoriously difficult to compute with STO basis sets since no analytical techniques are available and one has to resort to numerical methods. This explains why these functions, which were used in the early days of computational quantum chemistry, do not play any role in modem wave function based quantum chemical programs. Rather, in an attempt to have the cake and eat it too, one usually employs the so-called contracted GTO basis sets, in which several primitive Gaussian functions (typically between three and six and only seldom more than ten) as in equation (7-19) are combined in a fixed linear combination to give one contracted Gaussian function (CGF),... 

In Appendix A2, we have formally applied the perturbation method to find the energy levels of a d ion in an octahedral environment, considering the ligand ions as point charges. However, in order to understand the effect of the crystalline field over d ions, it is very illustrative to consider another set of basis functions, the d orbitals displayed in Figure 5.2. These orbitals are real functions that are derived from the following linear combinations of the spherical harmonics ... 

There are two approaches to map crystal charge density from the measured structure factors by inverse Fourier transform or by the multipole method [32]. Direct Fourier transform of experimental structure factors was not useful due to the missing reflections in the collected data set, so a multipole refinement is a better approach to map charge density from the measured structure factors. In the multipole method, the crystal charge density is expanded as a sum of non-spherical pseudo-atomic densities. These consist of a spherical-atom (or ion) charge density obtained from multi-configuration Dirac-Fock (MCDF) calculations [33] with variable orbital occupation factors to allow for charge transfer, and a small non-spherical part in which local symmetry-adapted spherical harmonic functions were used. 

More advanced mathematical aspects of aromaticity are given in other references [33, 34]. Some alternative methods beyond the scope of this chapter for the study of aromaticity in deltahedral molecules include tensor surface harmonic theory [35-38] and the related Hirsch 2 N -b 1) electron-counting rule for spherical aromaticity [39]. The topological solitons of nonlinear field theory related to the Skyrmions of nuclear physics have also been used to describe aromatic cluster molecules [40]. 

At the restoration stage, a one-center expansion in the spherical harmonics with numerical radial parts is most appropriate both for orbitals (spinors) and for the description of external interactions with respect to the core regions of a considered molecule. In the scope of the discussed two-step methods for the electronic structure calculation of a molecule, finite nucleus models and quantum electrodynamic terms including, in particular, two-electron Breit interaction may be taken into account without problems [67]. 

Variational one-center restoration. In the variational technique of one-center restoration (VOCR) [79, 80], the proper behavior of the four-component molecular spinors in the core regions of heavy atoms can be restored as an expansion in spherical harmonics inside the sphere with a restoration radius, Rvoa, that should not be smaller than the matching radius, Rc, used at the RECP generation. The outer parts of spinors are treated as frozen after the RECP calculation of a considered molecule. This method enables one to combine the advantages of two well-developed approaches, molecular RECP calculation in a gaussian basis set and atomic-type one-center calculation in numerical basis functions, in the most optimal way. This technique is considered theoretically in [80] and some results concerning the efficiency of the one-center reexpansion of orbitals on another atom can be found in [75]. 

In the point matching method (Oguchi, 1973 Bates, 1975) the fields inside and outside a particle are expanded in vector spherical harmonics and the resulting series truncated the tangential field components are required to be continuous at a finite number of points on the particle boundary. Although easy to describe and to understand, the practical usefulness of this method is limited to nearly spherical particles large demands on computer time and uncertain convergence are also drawbacks (Yeh and Mei, 1980). 

Physics texts often introduce spherical harmonics by applying the technique of separation of variables to a differential equation with spherical symmetry. This technique, which we will apply to Laplace s equation, is a method physicists use to hnd solutions to many differential equations. The technique is often successful, so physicists tend to keep it in the top drawer of their toolbox. In fact, for many equations, separation of variables is guaranteed to find all nice solutions, as we prove in Proposition A.3. 

Since spherical harmonics are functions from the sphere to the complex numbers, it is not immediately obvious how to visualize them. One method is to draw the domain, marking the sphere with information about the value of the function at various points. See Figure 1.8. Another way to visualize spherical harmonics is to draw polar graphs of the Legendre functions. See Figure 1.9. Note that for any , m we have F ,m = , the Legendre function carries all the information about the magnitude of the spherical harmonic. 

Spherical harmonics are derived from solutions of Laplace s equation ih spherical coordinates using the method of separation of variables—i.e., a solution of the form... 

Quantitative evaluation of a force-distance curve in the non-contact range represents a serious experimental problem, since most of the SFM systems give deflection of the cantilever versus the displacement of the sample, while the experimentalists wants to obtain the surface stress (force per unit contact area) versus tip-sample separation. A few prerequisites have to be met in order to convert deflection into stress and displacement into tip-sample separation. First, the point of primary tip-sample contact has to be determined to derive the separation from the measured deflection of the cantilever tip and the displacement of the cantilever base [382]. Second, the deflection can be converted into the force under assumption that the cantilever is a harmonic oscillator with a certain spring constant. Several methods have been developed for calibration of the spring constant [383,384]. Third, the shape of the probe apex as well as its chemical structure has to be characterised. Spherical colloidal particles of known radius (ca. 10 pm) and composition can be used as force probes because they provide more reliable and reproducible data compared to poorly defined SFM tips [385]. 

All of these hexafluorides are dimorphic, with a high-temperature, cubic form and an orthorhombic form, stable below the transition temperature (92). The cubic form corresponds to a body-centered arrangement of the spherical units, with very high thermal disorder of the molecules in the lattice, leading to a better approximation to a sphere. Recently, the structures of the cubic forms of molybdenum (93) and tungsten (94) hexafluorides have been studied using neutron powder data, with the profile-refinement method and Kubic Harmonic analysis. In both compounds the fluorine density is nonuniformly distributed in a spherical shell of radius equal to the M—F distance. Thus, rotation is not completely free, and there is some preferential orientation of fluorine atoms along the axial directions. The M—F distances are the same as in the gas phase and in the orthorhombic form. 

This method requires only a crude structural model as a starting model. In this analysis, the starting model was a homogeneous spherical shell density for the carbon cage. As for the temperature factors of all atoms, an isotropic harmonic model was used an isotropic Gaussian distribution is presumed for a La atom in the starting model. Then, the radius of the C82 sphere was refined as structural parameter in the Rietveld refinement. 

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