Beyond Hartree-Fock: MP2 and Coupled-Cluster Methods for large systems

Christof Hättig
Forschungszentrum Karslruhe, Institute of Nanotechnology, P. O. Box 3640, D-76021 Karlsruhe, Germany

In: Computational Nanoscience: Do It Yourself!, J. Grotendort, S. Blügel, D. Marx (Eds.), Institute for Advanced Simulation, Forschungszentrum Jülich, NIC Series, Vol 31, ISBN 3000173501, (2006).

This chapter reviews briefly the theory of second order Møller-Plesset perturbation theory (MP2), the approximate coupled-cluster singles-and-doubles method CC2 and closely related ab initio methods for calculations on excited states which treat the electron-electron interaction correctly through second order. It is shown how the computational costs (CPU time and storage requirements) can be reduced for these methods by orders of magnitudes using the resolution-of-the-identity approximation for electron repulsion integrals. The demands for the auxiliary basis sets are discussed and it is shown how with optimized basis sets the errors due to this approximation become insignificant compared to the usual orbital basis set error. Furthermore, a parallel implementation of RI-MP2 and RI-CC2 in the TURBOMOLE program package for distributed memory architectures (as e.g. clusters of linux boxes) is presented and some prototypical applications are reviewed.

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