A natural linear scaling coupled-cluster method

The Journal of Chemical Physics
Norbert Flocke, Rodney J Bartlett

Abstract

It is shown that using an appropriate localized molecular orbital (LMO) basis, one is able to calculate coupled-cluster singles and doubles (CCSD) wave functions and energies for very large systems by performing full CCSD calculations on small subunits only. This leads to a natural linear scaling coupled-cluster method (NLSCC), in which total correlation energies of extended systems are evaluated as the sum of correlation energy contributions from individual small subunits within that system. This is achieved by defining local occupied orbital correlation energies. These are quantities, which in the LMO basis become transferable between similar molecular fragments. Conventional small scale existing molecular CCSD codes are all that is needed, the local correlation effect being simply transmitted via the appropriate LMO basis. Linear scaling of electronic correlation energy calculations is thus naturally achieved using the NLSCC approach, which in principle can treat nonperiodic extended systems of infinite basis set size. Results are shown for alkanes and several polyglycine molecules and the latter compared to recent results obtained via an explicit large scale LCCSD calculation. (c) 2004 American Institute of Physics.

References

Apr 2, 2002·Journal of Computational Chemistry·Shuhua LiYuansheng Jiang

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Citations

May 7, 2010·Physical Chemistry Chemical Physics : PCCP·Ricardo A Mata
Jun 10, 2010·Physical Chemistry Chemical Physics : PCCP·Wibe A de JongRoland Lindh
Apr 12, 2012·Physical Chemistry Chemical Physics : PCCP·Christine Krause, Hans-Joachim Werner
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