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Computation of the Hartree-Fock Exchange by the Tensor-structured Methods |
| V. Khoromskaia |
| Max-Planck-Institute for Mathematics in the Sciences |
| Inselstr.~22-26, D-04103 Leipzig, Germany |
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Abstract :
We propose a novel numerical method for fast and accurate evaluation
of the exchange part of the Fock operator in the Hartree-Fock
equation which is a (nonlocal) integral operator in $\mathbb{R}^3
\times \mathbb{R}^3$. Usually, this challenging computational
problem is solved by analytical evaluation of two-electron
integrals using the ``analytically separable'' Galerkin basis
functions, like Gaussians. Instead, we employ the agglomerated
``grey-box'' numerical computation of the corresponding
six-dimensional integrals in the tensor-structured format which does
not require analytical separability of the basis set. The point of
our method is a low-rank tensor representation of arising functions
and operators on an $n\times n\times n$ Cartesian grid and the
implementation of the corresponding multi-linear algebraic
operations in the tensor product format. Linear scaling of the
tensor operations, including the 3D convolution product, with
respect to the one-dimension grid size $n$ enables computations on
huge 3D Cartesian grids thus providing the required high accuracy.
The presented algorithm for evaluation of the exchange operator and
a recent tensor method for the computation of the Coulomb matrix are
the main building blocks in the numerical solution of the
Hartree-Fock equation by the tensor-structured methods. These
methods provide a new tool for algebraic optimization of the
Galerkin basis in the case of large molecules.
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2000 MSC : 65F30, 65F50, 65N35, 65F10
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Keywords : Hartree-Fock operator, exchange matrix, canonical model, discrete tensor convolution, tensor-structured methods, tensor-product basis functions
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