Beyond the Dailey-Townes model: chemical information from the electric field gradient

TL;DR

This paper reexamines the Dailey-Townes model by analyzing electric field gradients in various compounds, revealing its limitations and proposing improvements through projection analysis and considering spin-orbit effects.

Contribution

The study provides a detailed decomposition of EFGs, highlights the model's shortcomings, and introduces modifications for better accuracy, especially with relativistic effects.

Findings

Dailey-Townes model deviates from actual EFGs in chlorine compounds.

Core polarization significantly contributes to EFG in uranyl.

Including spin-orbit interaction alters the EFG operator's properties.

Abstract

In this work, we reexamine the Dailey-Townes model by systematically investigating the electric field gradient (EFG) in various chlorine compounds, dihalogens, and the uranyl ion. Through the use of relativistic molecular calculations and projection analysis, we decompose the EFG expectaton value in terms of atomic reference orbitals. We show how the Dailey-Townes model can be seen as an approximation to our projection analysis. Moreover, we observe for the chlorine compounds that, in general, the Dailey-Townes model deviates from the total EFG value. We show that the main reason for this is that the Dailey-Townes model does not account for contributions from the mixing of valence p orbitals with subvalence ones. We also find a non-negligible contribution from core polarization. This can be interpreted as Sternheimer shielding, as discussed in an appendix. The predictions of the Dailey-Townes model are improved by replacing net populations by gross ones, but we have not found any theoretical justification for this. Subsequently, for the molecular systems XCl (where X = I, At, and Ts), we find that with the inclusion of spin-orbit interaction, the (electronic) EFG operator is no longer diagonal within an atomic shell, which is incompatible with the Dailey-Townes model. Finally, we examine the EFG at the uranium position in uranyl, where we find that about half the EFG comes from core polarization. The other half comes from the combination of the U-O bonds and the U(6p) orbitals, the latter mostly non-bonding, in particular with spin-orbit interaction included. The analysis was carried out with molecular orbitals localized according to the Pipek-Mezey criterion. Surprisingly, we observed that core orbitals are also rotated during this localization procedure, even though they are fully localized. We show in an appendix that, using this localization criterion, it is actually allowed.