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Perturbed atoms in molecules and solids: The PATMOS model

### Abstract

A new computational method for electronic-structure studies of molecules and solids is presented. The key element in the new model – denoted the perturbed atoms in molecules and solids model – is the concept of a perturbed atom in a complex. The basic approximation of the new model is unrestricted Hartree Fock (UHF). The UHF orbitals are localized by the Edmiston-Ruedenberg procedure. The perturbed atoms are defined by distributing the orbitals among the nuclei in such a way that the sum of the intra-atomic UHF energies has a minimum. Energy corrections with respect to the UHF energy, are calculated within the energy incremental scheme. The most important three- and four-electron corrections are selected by introducing a modified geminal approach. Test calculations are performed on N2, Li2, and parallel arrays of hydrogen atoms. The character of the perturbed atoms is illustrated by calculations on H2, CH4, and C6H6.

© 2013 AIP Publishing LLC

Received 13 March 2013
Accepted 31 July 2013
Published online 03 September 2013

Acknowledgments:
This work was supported by the Norwegian HPC project NOTUR that granted access to the supercomputer facilities in Norway.

Article outline:

I. INTRODUCTION
A. Determination of the PATMOS orbitals
A. Nitrogen molecule
A. Hydrogen molecule
1. A basis set restricted Hartree model
1. The general solution
1. The general solution
2. Definition of perturbed atoms
1. The general solution
2. Definition of perturbed atoms
1. The general solution
II. THE PATMOS MODEL
A. Determination of the PATMOS orbitals
1. A basis set restricted Hartree model
1. The general solution
1. The general solution
2. Definition of perturbed atoms
B. Intra-atomic correlation terms
B. Lithium molecule
B. Methane
1. The general solution
2. Definition of perturbed atoms
2. Numerical models
2. Numerical models
C. Diatomic correlation terms
1. The general solution
2. Numerical models
D. Triatomic correlation terms
E. Symmetry simplification
F. The PATMOS energy
G. Natural orbitals for poly-electron FCI
H. Localization measures
III. UHF FOR EXTENDED SYSTEMS
1. The general solution
2. Numerical models
C. Diatomic correlation terms
C. Arrays of hydrogen atoms
C. Benzene
1. The general solution
2. Numerical models
IV. TEST CALCULATIONS
A. Nitrogen molecule
B. Lithium molecule
C. Arrays of hydrogen atoms
D. Triatomic correlation terms
V. THE CHARACTER OF THE PERTURBED ATOMS
A. Hydrogen molecule
B. Methane
C. Benzene
E. Symmetry simplification
VI. CONCLUDING REMARKS
F. The PATMOS energy
G. Natural orbitals for poly-electron FCI
H. Localization measures

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/content/aip/journal/jcp/139/9/10.1063/1.4818577

2013-09-03

2016-10-23

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