Rigorous pKa Estimation of Amine Species Using Density-Functional Tight-Binding-Based Metadynamics Simulations

Aditya Wibawa Sakti, Yoshifumi Nishimura, Hiromi Nakai

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

Predicting pKa values for different types of amine species with high accuracy and efficiency is of critical importance for the design of high performance and economical solvents in carbon capture and storage with aqueous amine solutions. In this study, we demonstrate that density-functional tight-binding-based metadynamics simulations are a promising approach to calculate the free energy difference between the protonated and neutral states of amines in aqueous solution with inexpensive computational cost. The calculated pKa values were in satisfactory agreement with the experimental values, the mean absolute deviation being only 0.09 pKa units for 34 amines commonly used in CO2 scrubbing. Such superior reproducibility and correlation compared to estimations by static quantum mechanical calculations highlight the significant effect of dynamical proton transfer processes in explicit solvent molecules for the improvement of the estimation accuracy.

Original languageEnglish
Pages (from-to)351-356
Number of pages6
JournalJournal of Chemical Theory and Computation
Volume14
Issue number1
DOIs
Publication statusPublished - 2018 Jan 9

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Amines
amines
simulation
Carbon capture
Proton transfer
washing
Free energy
free energy
aqueous solutions
costs
deviation
Molecules
protons
carbon
Costs
molecules

ASJC Scopus subject areas

  • Computer Science Applications
  • Physical and Theoretical Chemistry

Cite this

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AB - Predicting pKa values for different types of amine species with high accuracy and efficiency is of critical importance for the design of high performance and economical solvents in carbon capture and storage with aqueous amine solutions. In this study, we demonstrate that density-functional tight-binding-based metadynamics simulations are a promising approach to calculate the free energy difference between the protonated and neutral states of amines in aqueous solution with inexpensive computational cost. The calculated pKa values were in satisfactory agreement with the experimental values, the mean absolute deviation being only 0.09 pKa units for 34 amines commonly used in CO2 scrubbing. Such superior reproducibility and correlation compared to estimations by static quantum mechanical calculations highlight the significant effect of dynamical proton transfer processes in explicit solvent molecules for the improvement of the estimation accuracy.

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