ISSN:
1432-2234
Keywords:
d andf polarisation functions
;
Optimisation of exponents
;
Electron correlation
Source:
Springer Online Journal Archives 1860-2000
Topics:
Chemistry and Pharmacology
Notes:
Summary The theory of Kutzelnigg and Klopper, which introduces the interelectronic co-ordinates into the first order Møller-Plesset wavefunction, requires diagonal matrix elements of the operators: $$\left\{ {r_{12} \times \frac{1}{{r_{12} }} - 1} \right\}$$ and $$\left\{ {r_{12} \times \frac{{r_{12} \cdot (\nabla _1 - \nabla _2 )}}{{4r_{12} }} + \frac{3}{4}} \right\}$$ These are evaluated through completeness insertions, and used to obtain corrections to pair energies which vanish as the one-particle basis set becomes complete. We suggest optimising exponents ofd andf polarisation functions to minimise these corrections, and have obtained 1d, 2d, 3d and 1f sets for B, C, N, O, F and Ne. These are compared with other sets reported in the literature.
Type of Medium:
Electronic Resource
URL:
http://dx.doi.org/10.1007/BF01117407
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