ADF has a fragment oriented approach: the poly-atomic system to be computed is conceptually built up from fragments, the molecular one-electron orbitals are calculated as linear combinations of fragment orbitals, and final analyzes of e.g. the bonding energy are in terms of fragment properties. The fragments may be single atoms or larger moieties.
When you compute a system in terms of its constituent fragments, these fragments must have been computed before and their properties must be passed on to the current calculation. This is done by attaching fragment files, which contain the necessary information. A fragment file is simply the standard result file of an ADF calculation on that fragment.
When using Basic Atoms as fragments, you do not need to create the fragment files yourself. Instead, you may use the Basis key, and ADF will create the required fragment files automatically. We therefore recommend this feature for starting ADF users.
Basic atoms
Obviously there must be a set of fundamental fragments that are not defined in terms of smaller fragments. Therefore ADF has two modes of execution: the normal mode, using fragments, and the create mode, in which a fundamental fragment is generated. Such a fundamental fragment must be a single atom, spherically symmetric and spin-restricted (i.e. spin-α and spin-β orbitals are spatially identical, they are equally occupied, and fractional occupations are applied, if necessary, to distribute the electrons equally over symmetry-degenerate states). Such a fundamental fragment is denoted a basic atom. The basic atoms are the smallest building blocks from which any 'real' calculations are started.
One should realize that the basic atoms are artificial objects that are convenient in the computational approach but that do not necessarily represent real atoms very well (in fact, usually not at all). The bonding energy of a molecule with respect to basic atoms, for instance, should be corrected for this discrepancy in order to get a decent comparison against experimental data. See ref. [1] for a discussion and for examples of applicable values.
A basic atom is computed in the conventional way. The one-electron orbitals are determined as linear combinations of basis functions; the frozen core approximation may be applied for the inner atomic states; a particular type of density functional can be chosen, et cetera. You may have, for instance, different basic Copper atoms by using different basis sets, by choosing different levels of frozen core approximations, or by applying different density functionals.
Slater-type basis sets
ADF uses Slater-Type Orbitals (STO's) as basis functions. Slaters can display the correct nuclear cusp and asymptotic decay.
f(r) = Ylmrne-ζr
The center of the function is at a nucleus, the Ylm are spherical harmonics, and the exponential factor ζ (zeta) determines the long-range decay of the function.
ADF has a database, which is included in the distribution, with thoroughly tested basis set files, ranging in quality from single-zeta to quadruple-zeta basis sets with various diffuse and polarization functions. All-electron and frozen-core basis sets are available for all elements, including lanthanides and actinides. The frozen-core approximation can be used to considerably reduce the computation time for systems with heavy nuclei, in a controlled manner.
Automatic mode
If you are using 'Basic Atom' fragments only, you do not need to prepare the corresponding fragment files yourself. Instead, add the BASIS block key to the ADF input, and ADF will generate all the required fragment files for you. This makes your job scripts and ADF inputs simpler, it ensures that consistent options for the create runs and molecular runs are used, and you will be sure that the fragment files used have been created by the same release of ADF.
