TY - JOUR
T1 - Toward accurate solvation dynamics of lanthanides and actinides in water using polarizable force fields
T2 - From gas-phase energetics to hydration free energies
AU - Marjolin, Aude
AU - Gourlaouen, Christophe
AU - Clavaguéra, Carine
AU - Ren, Pengyu Y.
AU - Wu, Johnny C.
AU - Gresh, Nohad
AU - Dognon, Jean Pierre
AU - Piquemal, Jean Philip
PY - 2012/5/3
Y1 - 2012/5/3
N2 - In this contribution, we focused on the use of polarizable force fields to model the structural, energetic, and thermodynamical properties of lanthanides and actinides in water. In a first part, we chose the particular case of the Th(IV) cation to demonstrate the capabilities of the AMOEBA polarizable force field to reproduce both reference ab initio gas-phase energetics and experimental data including coordination numbers and radial distribution functions. Using such model, we predicted the first polarizable force field estimate of Th(IV) solvation free energy, which accounts for -1,638 kcal/mol. In addition, we proposed in a second part of this work a full extension of the SIBFA (Sum of Interaction Between Fragments Ab initio computed) polarizable potential to lanthanides (La(III) and Lu(III)) and to actinides (Th(IV)) in water. We demonstrate its capabilities to reproduce all ab initio contributions as extracted from energy decomposition analysis computations, including many-body charge transfer and discussed its applicability to extended molecular dynamics and its parametrization on high-level post-Hartree-Fock data.
AB - In this contribution, we focused on the use of polarizable force fields to model the structural, energetic, and thermodynamical properties of lanthanides and actinides in water. In a first part, we chose the particular case of the Th(IV) cation to demonstrate the capabilities of the AMOEBA polarizable force field to reproduce both reference ab initio gas-phase energetics and experimental data including coordination numbers and radial distribution functions. Using such model, we predicted the first polarizable force field estimate of Th(IV) solvation free energy, which accounts for -1,638 kcal/mol. In addition, we proposed in a second part of this work a full extension of the SIBFA (Sum of Interaction Between Fragments Ab initio computed) polarizable potential to lanthanides (La(III) and Lu(III)) and to actinides (Th(IV)) in water. We demonstrate its capabilities to reproduce all ab initio contributions as extracted from energy decomposition analysis computations, including many-body charge transfer and discussed its applicability to extended molecular dynamics and its parametrization on high-level post-Hartree-Fock data.
KW - Actinides
KW - Charge transfer
KW - Energy decomposition analysis
KW - Hydration free energy
KW - Lanthanides
KW - Polarizable force field
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U2 - 10.1007/s00214-012-1198-7
DO - 10.1007/s00214-012-1198-7
M3 - Article
AN - SCOPUS:84860343588
SN - 1432-881X
VL - 131
SP - 1
EP - 14
JO - Theoretical Chemistry Accounts
JF - Theoretical Chemistry Accounts
IS - 4
M1 - 1198
ER -