Journal
JOURNAL OF CHEMICAL THEORY AND COMPUTATION
Volume 10, Issue 8, Pages 3055-3065Publisher
AMER CHEMICAL SOC
DOI: 10.1021/ct5002736
Keywords
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Funding
- Beatriu de Pinos program from AGAUR [BP_A_00339, BP_B_00236]
- EU under the Marie Curie Career Integration grant [PCI09-GA-2011-294240]
- Spanish MINECO Europa Excelencia project [CTQ2013-41236-ERC]
- Spanish MICINN Project [CTQ2011-23156/BQU]
- Catalan DIUE [2009SGR637, 2009SGR528]
- Xarxa de Referencia en Quimica Teorica i Computacional
- FEDER [UNGI08-4E-003]
- DIUE of the Generalitat de Catalunya
- Centre de Supercomputacio de Catalunya (CESCA)
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In this work we present the formulas for the calculation of exact three-center electron sharing indices (3c-ESI) and introduce two new approximate expressions for correlated wave functions. The 3c-ESI uses the third-order density, the diagonal of the third-order reduced density matrix, but the approximations suggested in this work only involve natural orbitals and occupancies. In addition, the first calculations of 3c-ESI using Valdemoro's, Nakatsuji's and Mazziotti's approximation for the third-order reduced density matrix are also presented for comparison. Our results on a test set of molecules, including 32 3c-ESI values, prove that the new approximation based on the cubic root of natural occupancies performs the best, yielding absolute errors below 0.07 and an average absolute error of 0.015. Furthemore, this approximation seems to be rather insensitive to the amount of electron correlation present in the system. This newly developed methodology provides a computational inexpensive method to calculate 3c-ESI from correlated wave functions and opens new avenues to approximate high-order reduced density matrices in other contexts, such as the contracted Schrodinger equation and the anti-Hermitian contracted Schrodinger equation.
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