Basis Set

AICCM uses the linear combination of atomic orbitals (LCAO) approach and uses contracted gaussian as basis functions.

Notation

1. Unnormalized primitive Cartesian Gaussian function centered at A.

(x-A_x)^n_x

2) A set of functions with the same angular momentum, located at a common center but with different n form a Cartesian shell. The order of functions that AICCM uses is the same as in LIBINT.

s : s

p : p_x, p_y, p_z

d : d_xx, d_xy, d_xz, d_yy, d_yz, d_zz

f : f_xxx, f_xxy, f_xxz, f_xyy, f_xyz, f_x_zz, f_yyy, f_yyz, f_yyz, f_zzz

When we add a set of d orbitals to the basis set, you might expect that we add five additional functions - dxy, dxz, dyz, dx2-y2 and dz2. These are called the sperical harmonic or just spherical d orbitals. However, there is another way. It is usual to calculate the integrals using the set - dxy, dxz, dyz, dx2, dy2 and dz2. These 6 orbitals are not independent. There are really only 5 d orbitals. Combinations of these 6 give the 5 true d orbitals and one - dx2 + dy2 + dz2 which is really a spherical s-type orbital. This arises since x2 + y2 + z2 = r2.

The d orbitals have the form:

xy exp(-ar2)

for dxy, and so on.

These 6 orbitals are called the cartesian d orbitals and they are used to build the 5 spherical d orbitals if we decide to use the spherical d orbitals. We normally have a choice and in many cases we decide to use the simpler cartesian d orbitals and this can be quicker even though the basis set is larger. They also of course in effect add an additional s orbital which will lower the energy slightly.

Automatic Generation of an Auxiliary Basis

Generates an auxiliary function set from the orbital basis exponents by a geometric progression. This function is loosely based on the function implemented in deMon [1]. The things that are different are only for better readability and to do it in a more pythonic way. Everything concerning ECP/MCP was removed since we do not have ECP/MCP support (yet?). The algorithm is described in the deMon manual [2].

Generate-An with n from 1 to 4 or 2* to 4*:

A1: H-Xe: s

A2 to A4: H-He: s

Li-Xe: s, spd

A2* to A4*: H-He: s, spd

Li-Xe: s, spd, spdfg

[1] deMon2k, A.M. Köster, G. Geudtner, P. Calaminici,

M.E. Casida, V.D. Dominguez, R. Flores-Moreno, A. Goursot, T. Heine, A. Ipatov, F. Janetzko, J.M. del Campo, J. U. Reveles, A. Vela, B. Zuniga and D.R. Salahub, The deMon Developers, CINVESTAV, Mexico (2011).

[2] The deMon2k Users’ Guide Installation and Reference Manual