Accurate and efficient algorithm for Bader charge integration

Unknown author(s)

The Journal of Chemical Physics · 2011 · 2K citations · 16 references

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Concepts

TL;DR

The study proposes an efficient, accurate method for integrating basins of attraction on a general discrete grid, applied to Bader charge partitioning of electron charge density. The method follows charge‑density gradient trajectories to compute the fraction of space flowing to each grid point, enabling calculation of Bader volumes and discrete integration weights, and can be extended to nonuniform grids. Compared to other grid‑based algorithms, the approach is robust, computationally efficient with linear effort, accurate, and converges quadratically.

Abstract

We propose an efficient, accurate method to integrate the basins of attraction of a smooth function defined on a general discrete grid and apply it to the Bader charge partitioning for the electron charge density. Starting with the evolution of trajectories in space following the gradient of charge density, we derive an expression for the fraction of space neighboring each grid point that flows to its neighbors. This serves as the basis to compute the fraction of each grid volume that belongs to a basin (Bader volume) and as a weight for the discrete integration of functions over the Bader volume. Compared with other grid-based algorithms, our approach is robust, more computationally efficient with linear computational effort, accurate, and has quadratic convergence. Moreover, it is straightforward to extend to nonuniform grids, such as from a mesh-refinement approach, and can be used to both identify basins of attraction of fixed points and integrate functions over the basins.

References

16