A Guided Stochastic Energy-Domain Formulation of the Second Order Møller-Plesset Perturbation Theory.
We develop an alternative formulation in the energy-domain to calculate the second order Møller-Plesset (MP2) perturbation energies. The approach is based on repeatedly choosing four random energies using a nonseparable guiding function, filtering four random orbitals at these energies, and averaging the resulting Coulomb matrix elements to obtain a statistical estimate of the MP2 correlation energy. In contrast to our time-domain formulation, the present approach is useful for both quantum chemistry and real-space/plane wave basis sets. The scaling of the MP2 calculation is roughly linear with system size, providing a useful tool to study dispersion energies in large systems. This is demonstrated on a structure of 64 fullerenes within the SZ basis as well as on silicon nanocrystals using real-space grids.
†Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.|‡Department of Chemistry, Zhejiang University, 38 Zheda Road, Hangzhou, China, 310027.
Qinghui
Q
Ge
†Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.
Yi
Y
Gao
§Fritz Haber Center for Molecular Dynamics, Institute of Chemistry, The Hebrew University of Jerusalem, Jerusalem 91904, Israel.
Roi
R
Baer
∥School of Chemistry, The Sackler Faculty of Exact Sciences, Tel Aviv University, Tel Aviv 69978, Israel.
Eran
E
Rabani
†Department of Chemistry and Biochemistry, University of California, Los Angeles, California 90095, United States.
Daniel
D
Neuhauser
MP2; linear scaling; quantum chemistry; stochastic; van der Waals