The role of basis set superposition error in water addition reactions to Ln(III) cations

Abstract

Our goal in this work was to characterize the importance of basis set superposition error (BSSE) in the reaction energetics of water addition to highly charged metal ions that exhibit strong ion-dipole interactions with water. The gas phase water addition reactions, M([M ϭ La(III), Lu(III); N ϭ 0 -8] have been studied, with a particular emphasis on a posteriori methods for calculating BSSE and its constituent energetic components as a function of M(H 2 O) N 3ϩ cluster size and water basis set. Because of accumulation of BSSE within the subclusters in the reaction series, the successive reaction counterpoise method for determining the BSSE correction interaction energies is advocated.

Toward the Prediction of Water Exchange Rates in Magnetic Resonance Imaging Contrast Agents: A Density Functional Theory Study

“…Previous studies have shown that LCRECP calculations provide somewhat longer bond distances of the metal coordination environment than computations based on the SCRECP approach. − Our results are in line with these studies, as SCRECP calculations give bond distances typically 0.04–0.06 Å shorter than the LCRECP counterparts (Figure and Figures S1–S7, Supporting Information). However, the values of the electron localization function (ELF), the electron density (ρ), and its Laplacian (∇ 2 ρ) obtained with LC and SC calculations for Gd complexes are very similar (see below).…”

Density functional dependence of molecular geometries in lanthanide(III) complexes relevant to bioanalytical and biomedical applications

“…The trend followed by the bond distances is reproduced reasonably well by all functionals explored. However, use of LSDA functionals provides very short bond distances, in line with previous studies that showed that these functionals often predict overbinding [35,42] . On the contrary, GGA functionals such as G96LYP provide significantly longer distances than MP2, a situation also observed for Ln-N bonds with the use of hybrid-GGA functionals.…”

“…A detailed investigation of the structural and thermodynamic features of Ln III aqua-ions has been recently reported. The structural parameters calculated for [Ln(H 2 O) 8 ] 3+ (Ln = La or Lu) indicated also overbinding when using LSDA functionals [42] . Among the functionals tested in these studies the meta-GGA TPSS functional provided the closest structural agreement with experimental results, while the performance of the hybrid B3LYP functional was also reasonable [43] .…”

Sensitivity of Solvation Environment to Oxidation State and Position in the Early Actinide Period

“…This protocol enables a partial accounting of configurational sampling within the clusters because different configurations that have the same number of H bonds have very close energies. Counterpoise corrections were not included in eq to correct for basis set superposition error, as prior studies have shown that the magnitude of the correction is minimal compared to water binding energies to trivalent lanthanides . For instructive purposes, the implementation of the calculation of Δ G solv in a thermochemical cycle is presented in Figure S1 in the Supporting Information.…”