Lowdin-type orbitals

Boys [1950] introduced particular gaussian function orbital representations as replacements for the Slater-type orbitals employed almost exclusively until that point in time. Lowdin s [1955] natural orbitals had a simple quantum-mechanical interpretation as well as rapid convergence... 

A simple and robust quantitative MO-type approach (as opposed to density approaches) is the ubiquitous Mulliken population analysis [40]. The key concept of this easily programmed and fast method is the distribution of electrons based on occupations of atomic orbitals. The atomic populations do not, however, include electrons from the overlap populations, which are divided exactly in the middle of the bonds, regardless of the bonding type and the electronegativity. As a consequence, differences of atom types are not properly accommodated and the populations per orbital can be larger than 2, which is a violation of the Pauli principle a simple remedy for this error is a Lowdin population analysis that... 

If the Hartree-Fock determinant dominates the wavefunction, some of the occupation numbers will be close to 2. The corresponding MOs are closely related to the canonical Hartree-Fock orbitals. The remaining natural orbitals have small occupation numbers. They can be analysed in terms of different types of correlation effects in the molecule . A relation between the first-order density matrix and correlation effects is not immediately justified, however. Correlation effects are determined from the properties of the second-order reduced density matrix. The most important terms in the second-order matrix can, however, be approximately defined from the occupation numbers of the natural orbitals. Electron correlation can be qualitatively understood using an independent electron-pair model . In such a model the correlation effects are treated for one pair of electrons at a time, and the problem is reduced to a set of two-electron systems. As has been shown by Lowdin and Shull the two-electron wavefunction is determined from the occupation numbers of the natural orbitals. Also the second-order density matrix can then be specified by means of the natural orbitals and their occupation numbers. Consider as an example the following simple two-configurational wavefunction for a two-electron system ... 

Lovasz-Pelikan index spectral indices (0 eigenvalues of the adjacency matrix) LOVIs = LOcal Vertex Invariants local invariants Lowdin population analysis quantum-chemical descriptors Lowest-Observed-Effect Level biological activity indices (0 toxicological indices) lowest unoccupied molecular orbital quantum-chemical descriptors lowest unoccupied molecular orbital energy quantum-chemical descriptors LUDI energy function scoring functions Lu index —> hyper-Wiener-type indices... 

The natural orbital concept, as originally formulated by Per-Olov Lowdin, refers to a mathematical algorithm by which bestpossible orbitals (optimal in a certain maximum-density sense) are determined from the system wavefunction itself, with no auxiliary as sumptions or input. Such orbitals inherently provide the most compact and efficient numerical description of the many-electron molecular wavefunction, but they harbor a type of residual multicenter indeterminacy (akin to that of Hartree-Fock molecular orbitals) that somewhat detracts from their chemical usefulness. 

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