Abstract
A formalism for the second-order Møller-Plesset perturbation method employing basis functions that depend explicitly on electron-electron distances (the MP2-R12 or F12 method) is derived and implemented into computer codes for extended systems periodic in one dimension. The excitation amplitudes on these functions are held fixed at values that satisfy the first-order cusp condition. Necessary many-electron integrals over Gaussian-type functions involving Slater-type geminals are evaluated by means of the resolution-of-the-identity approximation with a complementary auxiliary basis set. These integrals and thus the final correlation energy are shown to have the correct size dependence. The valence MP2 correlation energy of polyethylene near the complete basis-set limit is obtained and shown to be considerably greater in magnitude than the value obtained without the R12 treatment.
| Original language | English (US) |
|---|---|
| Article number | 151101 |
| Journal | Journal of Chemical Physics |
| Volume | 132 |
| Issue number | 15 |
| DOIs | |
| State | Published - Apr 21 2010 |
Funding
T.S. is indebted to Professor Edward F. Valeev for helpful discussions. T.S. is financially supported by a Japan Society for the Promotion of Science Research Fellowship for Young Scientists. S.H. thanks Department of Energy (Grant No. ), the Donors of the American Chemical Society Petroleum Research Fund (Grant No. ), and National Science Foundation (Grant No. ). S.H. is a Camille Dreyfus Teacher-Scholar. This research was supported in part by the National Science Foundation through TeraGrid resources provided by NCSA.
ASJC Scopus subject areas
- General Physics and Astronomy
- Physical and Theoretical Chemistry