Comparative CHARMM and AMOEBA Simulations of Lanthanide Hydration Energetics and Experimental Aqueous-Solution Structures

Baofu Qiao*, S. Skanthakumar, L. Soderholm

*Corresponding author for this work

Research output: Contribution to journalArticlepeer-review

10 Scopus citations

Abstract

The accurate understanding of metal ion hydration in solutions is a prerequisite for predicting stability, reactivity, and solubility. Herein, additive CHARMM force field parameters were developed to enable molecular dynamics simulations of lanthanide (Ln) speciation in water. Quantitatively similar to the much more resource-intensive polarizable AMOEBA potential, the CHARMM simulations reproduce the experimental hydration free energies and correlations in the first shell (Ln-oxygen distance and hydration number). Comparisons of difference pair-distribution functions obtained from the two simulation approaches with those from high-energy X-ray scattering experiments reveal good agreement of first-coordination sphere correlations for the Lu3+ ion (CHARMM only), but further improvement to both approaches is required to reproduce the broad, non-Gaussian distribution seen from the La3+ experiment. Second-coordination sphere comparisons demonstrate the importance of explicitly including an anion in the simulation. This work describes the usefulness of less resource-intensive additive potentials in some complex chemical systems such as solution environments where multiple interactions have similar energetics. In addition, 3-dimensional descriptions of the La3+ and Lu3+ coordination geometries are extracted from the CHARMM simulations and generally discussed in terms of potential improvements to solute-structure modeling within solution environments.

Original languageEnglish (US)
Pages (from-to)1781-1790
Number of pages10
JournalJournal of Chemical Theory and Computation
Volume14
Issue number3
DOIs
StatePublished - Mar 13 2018

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

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