Evaluation of Density-Functional Tight-Binding Methods for Simulation of Protic Molecular Ion Pairs

Tyler Walker; Van Quan Vuong; Stephan Irle; Jihong Ma

doi:10.1002/jcc.70064

Evaluation of Density-Functional Tight-Binding Methods for Simulation of Protic Molecular Ion Pairs

Tyler Walker
, Van Quan Vuong
, Stephan Irle
, Jihong Ma

Computational Chemistry and Nanomaterial

Research output: Contribution to journal › Article › peer-review

Abstract

In this work, we benchmark the accuracy of the density-functional tight-binding (DFTB) method, namely the long-range corrected second-order (LC-DFTB2) and third-order (DFTB3) models, for predicting energetics of imidazolium-based ionic liquid (IL) ion pairs. We compare the DFTB models against popular density functionals such as LC-ωPBE and B3LYP, using ab initio domain-based local pair-natural orbital coupled cluster (DLPNO-CC) energies as reference. Calculations were carried out in the gas phase, as well as in aqueous solution using implicit solvent methods. We find that the LC-DFTB2 model shows excellent performance in the gas phase and agrees well with reference energies in implicit solvent, often outperforming DFTB3 predictions for complexation energetics. Our study identifies a range of opportunities for use of the LC-DFTB method and quantifies its sensitivity to protonation states and the types of chemical interactions between ion pairs.

Original language	English
Article number	e70064
Journal	Journal of Computational Chemistry
Volume	46
Issue number	5
DOIs	https://doi.org/10.1002/jcc.70064
State	Published - Feb 15 2025

Funding

T.W. acknowledges the support of an Energy Science and Engineering Fellowship from the Bredesen Center for Interdisciplinary Research and Graduate Education at the University of Tennessee, Knoxville. J.M. acknowledges the support of the National Science Foundation (NSF 2132055) and the U.S. Department of Energy (DE‐SC0023473). The calculations in this work were in part supported by the Office of Materials and Chemical Technologies within the Office of Nuclear Energy, US Department of Energy. This research used resources of the Compute and Data Environment for Science (CADES) at the Oak Ridge National Laboratory, which is supported by the Office of Science of the US Department of Energy under (DE‐AC05‐00OR22725). This work was supported by the US Department of Energy, (Grants DE‐AC05‐00OR22725 and DE‐SC0023473), National Science Foundation (Grant 2132055), and the University of Tennessee, Knoxville, Energy Science and Engineering Fellowship. Funding:

Keywords

benchmarks
density-functional tight-binding methods
ion pairs
ionization potentials
proton transfer

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title = "Evaluation of Density-Functional Tight-Binding Methods for Simulation of Protic Molecular Ion Pairs",

abstract = "In this work, we benchmark the accuracy of the density-functional tight-binding (DFTB) method, namely the long-range corrected second-order (LC-DFTB2) and third-order (DFTB3) models, for predicting energetics of imidazolium-based ionic liquid (IL) ion pairs. We compare the DFTB models against popular density functionals such as LC-ωPBE and B3LYP, using ab initio domain-based local pair-natural orbital coupled cluster (DLPNO-CC) energies as reference. Calculations were carried out in the gas phase, as well as in aqueous solution using implicit solvent methods. We find that the LC-DFTB2 model shows excellent performance in the gas phase and agrees well with reference energies in implicit solvent, often outperforming DFTB3 predictions for complexation energetics. Our study identifies a range of opportunities for use of the LC-DFTB method and quantifies its sensitivity to protonation states and the types of chemical interactions between ion pairs.",

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N2 - In this work, we benchmark the accuracy of the density-functional tight-binding (DFTB) method, namely the long-range corrected second-order (LC-DFTB2) and third-order (DFTB3) models, for predicting energetics of imidazolium-based ionic liquid (IL) ion pairs. We compare the DFTB models against popular density functionals such as LC-ωPBE and B3LYP, using ab initio domain-based local pair-natural orbital coupled cluster (DLPNO-CC) energies as reference. Calculations were carried out in the gas phase, as well as in aqueous solution using implicit solvent methods. We find that the LC-DFTB2 model shows excellent performance in the gas phase and agrees well with reference energies in implicit solvent, often outperforming DFTB3 predictions for complexation energetics. Our study identifies a range of opportunities for use of the LC-DFTB method and quantifies its sensitivity to protonation states and the types of chemical interactions between ion pairs.

AB - In this work, we benchmark the accuracy of the density-functional tight-binding (DFTB) method, namely the long-range corrected second-order (LC-DFTB2) and third-order (DFTB3) models, for predicting energetics of imidazolium-based ionic liquid (IL) ion pairs. We compare the DFTB models against popular density functionals such as LC-ωPBE and B3LYP, using ab initio domain-based local pair-natural orbital coupled cluster (DLPNO-CC) energies as reference. Calculations were carried out in the gas phase, as well as in aqueous solution using implicit solvent methods. We find that the LC-DFTB2 model shows excellent performance in the gas phase and agrees well with reference energies in implicit solvent, often outperforming DFTB3 predictions for complexation energetics. Our study identifies a range of opportunities for use of the LC-DFTB method and quantifies its sensitivity to protonation states and the types of chemical interactions between ion pairs.

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KW - ionization potentials

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Evaluation of Density-Functional Tight-Binding Methods for Simulation of Protic Molecular Ion Pairs

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