A Choice of Basis Sets

TABLE 4.3. High Symmetry Points for the SC Real-Space Lattice Cube 

BCC real-space lattices are completely determined by the condition that each inner vector, k, go over into another by all the symmetry operations. This is not the case for the tmncated octahedron. The surface of the Wigner-Seitz cell is only fixed at the truncating planes, not the octahedral planes. Nonetheless, the volume enclosed by the truncated octahedron is taken to be the first BZ for the FCC real-space lattice (Bouckaert et ak, 1936). The special high-symmetry points are shown in Table 4.5. 

The one-electron wave function in an extended solid can be represented with different basis sets. Discussed here are only two types, representing opposite extremes the plane-wave basis set (free-electron and nearly-free-electron models) and the Bloch sum of atomic orbitals basis set (LCAO method). A periodic solid may be considered constmcted by the coalescence of these isolated atoms into extended Bloch-wave functions. On the other hand, within the free-electron framework, in the limit of an infinitesimal periodic potential (V = 0), a Bloch-wave function becomes a simple 

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In addition to a choice of coordinate frames we have a choice of basis sets. For atomic p-orbitals we could choose the atomic basis set defined by the magnetic quantum numbers m, i.e. po), Pi) and p-i), or by the... 

When calculating the wavefunction it is important to make a choice of basis set J. t that is suitable for the available computing power and the accuracy desired. A straightforward early approach to basis set construction was to fit an accurate Slater-type atomic orbital (STO) with n gaussians,called STO- G. The quality of STO- G wavefunctions increases as n increases. It was determined that = 3 was a good starting point, and the STO-3G basis set has been widely used, particularly where computing resources were limited or for lai er molecules. 

A choice of basis set implies a partitioning of the Hamiltonian, H = Hel -I- Hso + Tn(R) + Hrot, into two parts a part, H ° which is fully diagonal in the selected basis set, and a residual part, H(1b The basis sets associated with the various Hund s cases reflect different choices of the parts of H that are included in fP°). Although in principle the eigenvalues of H are unaffected by the choice of basis, as long as this basis set forms a complete set of functions, one basis set is usually more convenient to use or better suited than the others for a particular problem. Convenience is a function of both the nature of the computational method and the relative sizes of electronic, spin-orbit, vibrational, and rotational energies. The angular momentum basis sets, from which Hund s cases (a)-(e) bases derive, are... 

To solve the Kohn-Sham equations a number of different approaches and strategies have been proposed. One important way in which these can differ is in the choice of basis set for expanding the Kohn-Sham orbitals. In most (but not all) DPT programs for calculating the properties of molecular systems (rather than for solid-state materials) the Kohn-Sham orbitals are expressed as a linear combination of atomic-centred basis functions ... 

The choice of basis set in ab initio calculations has been the subject of numerous theoretical studies. Early SCF calculations utilized mainly spht-va-lence basis sets such as 3-21G and 4-31G. The importance of inclusion of d polarization functions on sulfur atoms has been stressed by several authors. For instance, Suleimenov and Ha found that the omission of d polarization functions leads to a substantially lower barrier for the internal rotation ( 16 kj mol for the central bond of H2S4) and produces an unreahstically large S-S bond length for the most stable rotamer [4]. In general, the use of... 

For practical implementations it is necessary to represent the molecular electronic wave functions as a linear combination of some convenient set of basis functions. In principle any choice of basis set is permissible although the basis set must span any electronic configuration of the molecule. This implies that the basis must form a complete set. 

A determined by X-ray crystallography [56], whereas the distance to the amine groups deviates less, 2.09 A in this work and 2.01 A experimentally. Previous theoretical studies by Carloni et al. [63] and Zhang et al. [64] yielded Pt-Cl distances of 2.34 and 2.37 A, respectively. The difference from the more recently obtained value is related to the choice of basis set and exchange-correlation functional. 

At this point we should mention that we encountered instability problems in the linear response calculations for some of the MCSCF wavefunctions at intemuclear distances larger than R—S a.u. We believe those instabilities to be artifacts of the calculations because their existence or position depends on the choice of basis set, active space or number of electrons allowed in the RAS3 space. This implies that even though it might not be possible to generate... 

In this form, it becomes possible to analyze the merits of Mulliken charge distributions in comparisons with physical observables. Namely, we want to learn the true value of n and the appropriate value of A for given choices of basis sets. Three approaches were followed to this end ... 

These systems provide a useful example because the calculations often work, but occasionally fail, either by distortion from planarity or by failure to locate a stable minimum for one of the tautomers. Thus, the students learn to consider their results critically with a healthy dose of skepticism, to analyze the success or failure of the calculation, to consider the influence of the choice of method (semi-empirical or ab initio), to consider the influence of the choice of basis set, and to determine the answer to the research question posed. 

Since the second term is constant for a given geometry, the total energy depends on the choice of basis set through the HF energy. This dependence is illustrated in Table 2.1. 

The dimension of the secular determinant for a given molecule depends on the choice of basis set. EHT adopts two critical conventions. First, all core electrons are ignored. It is assumed that core electrons are sufficiently invariant to differing chemical environments that changes in their orbitals as a function of environment are of no chemical consequence, energetic or otherwise. All modern semiempirical methodologies make this approximation. In EHT calculations, if an atom has occupied d orbitals, typically the highest occupied level of d orbitals is considered to contribute to the set of valence orbitals. 

Having discussed ways to reduce the scope of the MCSCF problem, it is appropriate to consider the other limiting case. What if we carry out a CASSCF calculation for all electrons including all orbitals in the complete active space Such a calculation is called full configuration interaction or full CF. Witliin the choice of basis set, it is the best possible calculation that can be done, because it considers the contribution of every possible CSF. Thus, a full CI with an infinite basis set is an exact solution of the (non-relativistic, Bom-Oppenheimer, time-independent) Schrodinger equation. 

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