An analysis of two local measures of the electronic localization: a comparison with the ELF and the exchange-correlation density results

作者：Rincon Luis; Alvarellos Jose E; Almeida Rafael^*

来源：Physical Chemistry Chemical Physics, 2011, 13(20): 9498-9506.

DOI：10.1039/c0cp02711a

In this work we have explored the performance of two functions, recently proposed by Ayers [J. Chem. Sci., 2005, 117, 441], with the purpose of quantifying local electron localization. The first function, zeta(h), measures the total fluctuation per electron in the number of electrons at a given position r(1), while the second one, zeta(R), is a local representation of the minimum fluctuation criterion for electron localization. The study is carried out through a set of diatomic molecules that covers a wide range of covalent/polar character. Additionally, we have also calculated the electron localization function and the exchange-correlation hole along the internuclear axis. We have found that, for all the studied molecules, the numerical integration involved in computing zeta(h) did not converge. We think that this is so because the hole correlation calculations are not able to yield its correct asymptotic decaying behavior for large absolute values of the internuclear distances. On the other hand, the calculation of zeta(R) has proved to be feasible, and the information obtained from it has been concluded to be compatible to that rendered by the electron localization ELF) and the exchange-correlation density. Moreover, it has been also found that the results for zeta(R) allow to quantify the relative degree of electron localization within different molecular regions.

• 出版日期2011