Article (Scientific journals)
Ion-Hydroxyl Interactions: From High-Level Quantum Benchmarks to Transferable Polarizable Force Fields
Wineman-Fisher, Vered; Al-Hamdani, Yasmine; Addou, Iqbal et al.
2019In Journal of Chemical Theory and Computation, 154, p. 2444
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Abstract :
[en] Ion descriptors in molecular mechanics models are calibrated against reference data on ion–water interactions. It is then typically assumed that these descriptors will also satisfactorily describe interactions of ions with other functional groups, such as those present in biomolecules. However, several studies now demonstrate that this transferability assumption produces, in many different cases, large errors. Here we address this issue in a representative polarizable model and focus on transferability of cationic interactions from water to a series of alcohols. Both water and alcohols use hydroxyls for ion-coordination, and, therefore, this set of molecules constitutes the simplest possible case of transferability. We obtain gas phase reference data systematically from “gold-standard” quantum Monte Carlo and CCSD(T) methods, followed by benchmarked vdW-corrected DFT. We learn that the original polarizable model yields large gas phase water → alcohol transferability errors – the RMS and maximum errors are 2.3 and 5.1 kcal/mol, respectively. These errors are, nevertheless, systematic in that ion-alcohol interactions are overstabilized, and systematic errors typically imply that some essential physics is either missing or misrepresented. A comprehensive analysis shows that when both low- and high-field responses of ligand dipole polarization are described accurately, then transferability improves significantly – the RMS and maximum errors in the gas phase reduce, respectively, to 0.9 and 2.5 kcal/mol. Additionally, predictions of condensed phase transfer free energies also improve. Nevertheless, within the limits of the extrathermodynamic assumptions necessary to separate experimental estimates of salt dissolution into constituent cationic and anionic contributions, we note that the error in the condensed phase is systematic, which we attribute, at least, partially to the parametrization in long-range electrostatics. Overall, this work demonstrates a rational approach to boosting transferability of ionic interactions that will be applicable broadly to improving other polarizable and nonpolarizable models.
Disciplines :
Chemistry
Author, co-author :
Wineman-Fisher, Vered
Al-Hamdani, Yasmine
Addou, Iqbal
Tkatchenko, Alexandre ;  University of Luxembourg > Faculty of Science, Technology and Communication (FSTC) > Physics and Materials Science Research Unit
Varma, Sameer
External co-authors :
yes
Language :
English
Title :
Ion-Hydroxyl Interactions: From High-Level Quantum Benchmarks to Transferable Polarizable Force Fields
Publication date :
04 March 2019
Journal title :
Journal of Chemical Theory and Computation
ISSN :
1549-9618
eISSN :
1549-9626
Publisher :
American Chemical Society, United States - District of Columbia
Volume :
154
Pages :
2444
Peer reviewed :
Peer Reviewed verified by ORBi
Focus Area :
Physics and Materials Science
Computational Sciences
Available on ORBilu :
since 31 October 2019

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