A recently published alternative hierarchy of coupled-cluster approximations is reformulated as a perturbative correction. A single variant, a model for the total electronic energy based on the perfect quadruples model, is explored in detail. The computational scaling of the method developed is the same as canonical second order Møller–Plesset perturbation theory (fifth order in the number of molecular orbitals), but its accuracy competes with the high-accuracy, high-cost standard CCSD(T), even when the latter is allowed to break spin-symmetry. The variation presented can be implemented without explicit calculation and storage of the most expensive energy contributions, thereby improving the range of systems which can be treated. The performance and scaling of the method are demonstrated with calculations on the water, fluorine, and oxirane molecules, and compared to the parent model.
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21 April 2011
Research Article|
April 21 2011
The formulation and performance of a perturbative correction to the perfect quadruples model
John A. Parkhill;
John A. Parkhill
a)
University of California
, Berkeley, Berkeley, California 94720, USA
and Chemical Sciences Division, Lawrence Berkeley National Laboratory
, Berkeley, California 94720, USA
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Julian Azar;
Julian Azar
b)
University of California
, Berkeley, Berkeley, California 94720, USA
and Chemical Sciences Division, Lawrence Berkeley National Laboratory
, Berkeley, California 94720, USA
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Martin Head-Gordon
Martin Head-Gordon
c)
University of California
, Berkeley, Berkeley, California 94720, USA
and Chemical Sciences Division, Lawrence Berkeley National Laboratory
, Berkeley, California 94720, USA
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a)
Electronic mail: john.parkhill@gmail.com.
b)
Electronic mail: julianazar2323@berkeley.edu.
c)
Tel.: 510-642-5957. Fax: 510-643-1255. Electronic mail: mhg@cchem.berkeley.edu.
J. Chem. Phys. 134, 154112 (2011)
Article history
Received:
January 11 2011
Accepted:
April 05 2011
Citation
John A. Parkhill, Julian Azar, Martin Head-Gordon; The formulation and performance of a perturbative correction to the perfect quadruples model. J. Chem. Phys. 21 April 2011; 134 (15): 154112. https://doi.org/10.1063/1.3582729
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