Orbital exponents

Even-tempered basis sets [40] consist of GTOs in which tlie orbital exponents belonging to series of... 

ZINDO/1 IS based on a modified version of the in termediate neglect of differen tial overlap (IXDO), which was developed by Michael Zerner of the Quantum Theory Project at the University of Florida. Zerner s original INDO/1 used the Slater orbital exponents with a distance dependence for the first row transition metals only. Ilow ever. in HyperChein constant orbital expon en ts are used for all the available elein en ts, as recommended by Anderson. Friwards, and Zerner. Inorg. Chem. 2H, 2728-2732.iyH6. 

Once the least-squares fits to Slater functions with orbital exponents e = 1.0 are available, fits to Slater function s with oth er orbital expon cn ts can be obtained by siin ply m ii Itiplyin g th e cc s in th e above three equations by It remains to be determined what Slater orbital exponents to use in electronic structure calculation s. The two possibilities may be to use the "best atom" exponents (e = 1. f) for II. for exam pie) or to opiim i/e exponents in each calculation. The "best atom expon en ts m igh t be a rather poor ch oicc for mo lecular en viron men ts, and optirn i/.at ion of non linear exponents is not practical for large molecules, where the dimension of the space to be searched is very large.. 4 com prom isc is to use a set of standard exponents where the average values of expon en ts are optirn i/ed for a set of sin all rn olecules, fh e recom -mended STO-3G exponents are... 

Slater provided a series of empirical rules for choosing the orbital exponents (, which are... 

The orbital exponent 4 is expressed as a function of two parameters a and / as follows ... 

For first- and seeond-row atoms, the Is or (2s, 2p) or (3s,3p, 3d) valenee-state ionization energies (aj s), the number of valenee eleetrons ( Elee.) as well as the orbital exponents (es, ep and ej) of Slater-type orbitals used to ealeulate the overlap matrix elements Sp y eorresponding are given below. 

Even-tempered basis sets (M. W. Schmidt and K. Ruedenberg, J. Chem. Phys. 71, 3961 (1979)) consist of GTOs in which the orbital exponents ak belonging to series of orbitals consist of geometrical progressions ak = a, where a and P characterize the particular set of GTOs. 

The values of the orbital exponents ( s or as) and the GTO-to-CGTO eontraetion eoeffieients needed to implement a partieular basis of the kind deseribed above have been tabulated in several journal artieles and in eomputer data bases (in partieular, in the data base eontained in the book Handbook of Gaussian Basis Sets A. Compendium for Ab initio Moleeular Orbital Caleulations, R. Poirer, R. Kari, and I. G. Csizmadia, Elsevier Seienee Publishing Co., Ine., New York, New York (1985)). 

Table 3.1 Energy integrals for the hydrogen moleeule-ion LCAO problem. Reduced units are used throughout, f is the orbital exponent, and Rab the internuelear separation, p = Rab...

With the above in mind, it is sensible to modify the atomic orbital by treating the orbital exponent as a variational parameter. What we could do is vary for each value of the intemuclear separation 7 ab, and for each value of 7 ab calculate the energy with that particular orbital exponent. Just for illustration, I have calculated the energies for a range of orbital exponent and intemuclear distance pairs, and my results are shown as energy contours in Figure 3.3. 

Figure 3.3 Energy vs intemuclear distance and orbital exponent...

The horizontal axis corresponds to an intemuclear separation running from 1.5 to 2.5 flo and the vertical axis corresponds to an orbital exponent running from 1,0 to 1.4. The potential energy minimum corresponds to an exponent of 1.238, and we note the contraction of the atomic Is orbital on molecule formation. 

The orbital is correctly normalized. I have taken a bond length of 106 pm, and fixed the orbital exponent at 1. 

A slight improvement in the predicted dissociation energy occurs if the Is orbital exponent is treated as a variational parameter. 

It is instructive to look at the form of the Is, 2s and 3s orbitals (Table 9.1). By convention, we use the dimensionless variable p = Zrjaa rather than r. Here 2 is the nuclear charge number and oq the first Bohr radius (approximately 52.9 pm). The quantity Z/n is usually called the orbital exponent, written These exponents have an increasing number of radial nodes, and they are orthonormal. 

In honour of J. C. Slater, we refer to such basis functions as Slater-type orbitals (STOs). Slater orbital exponents ( = (Z — s)/n ) for atoms through neon are given in Table 9.2. 

Clementi and Raimondi refined these results by performing atomic HF-LCAO calculations, treating the orbital exponents as variational parameters. A selection of their results for H through Ne is given in Table 9.3. 

The self-consistent field function for atoms with 2 to 36 electrons are computed with a minimum basis set of Slater-type orbitals. The orbital exponents of the atomic orbitals are optimized so as to ensure the energy minimum. The analysis of the optimized orbital exponents allows us to obtain simple and accurate rules for the 1 s, 2s, 3s, 4s, 2p, 3p, 4p and 3d electronic screening constants. These rules are compared with those proposed by Slater and reveal the need for the screening due to the outside electrons. The analysis of the screening constants (and orbital exponents) is extended to the excited states of the ground state configuration and the positive ions. 

---