9 research outputs found
Comparison of localization procedures for applications in crystal embedding
With the aim of future applications in quantum mechanical embedding in
extended systems such as crystals, we suggest a simple and computationally
efficient method which enables construction of a set of nonorthogonal highly
localized one-electron orbitals for periodic nonmetallic crystals which reflect
their chemical nature. The orbitals are also used to build up the Hartree-Fock
(HF) electron density of the entire crystals. The simplicity of the method
stems from the fact that it does not require usage and/or modification of
periodic electronic structure codes, and is instead based on the HF calculation
of a sequence of finite clusters with subsequent application of a localization
procedure to transform the HF canonical molecular orbitals. Two extreme cases
of chemical bonding, ionic (MgO crystal) and covalent (Si crystal), are
considered for which a number of known localization schemes are applied and
compared. With some modifications our method can also be applied to nonperiodic
nonmetallic systems as well
Strongly localised molecular orbitals for -quartz
A previously proposed computational procedure for constructing a set of
nonorthogonal strongly localised one-electron molecular orbitals (O. Danyliv,
L. Kantorovich - physics/0401107) is applied to a perfect -quartz
crystal characterised by an intermediate type of chemical bonding. The orbitals
are constructed by applying various localisation methods to canonical
Hartree-Fock orbitals calculated for a succession of finite molecular clusters
of increased size with appropriate boundary conditions. The calculated orbitals
span the same occupied Fock space as the canonical HF solutions, but have an
advantage of reflecting the true chemical nature of the bonding in the system.
The applicability of several localisation techniques as well as of a number of
possible choices of localisation regions (structure elements) are discussed for
this system in detail
Calculation of electron density of periodic systems using non-orthogonal localised orbitals
Methods for calculating an electron density of a periodic crystal constructed
using non-orthogonal localised orbitals are discussed. We demonstrate that an
existing method based on the matrix expansion of the inverse of the overlap
matrix into a power series can only be used when the orbitals are highly
localised (e.g. ionic systems). In other cases including covalent crystals or
those with an intermediate type of chemical bonding this method may be either
numerically inefficient or fail altogether. Instead, we suggest an exact and
numerically efficient method which can be used for orbitals of practically
arbitrary localisation. Theory is illustrated by numerical calculations on a
model system.Comment: 12 pages, 4 figure