Assessment of dispersion-improved exchange-correlation functionals for the simulation of CO2 binding by alcoholamines

Hsueh Chien Li, Jeng Da Chai, Ming Kang Tsai

Research output: Contribution to journalArticle

9 Citations (Scopus)

Abstract

In this study, 12 bound complexes were selected to construct a database for testing 15 dispersion-improved exchange-correlation (XC) functionals, including hybrid generalized gradient approximation (GGA), modified using the Grimme's pairwise strategy, and double hybrid XC functionals, for specifically characterizing the CO2 binding by alcoholamines. Bound complexes were selected based on the characteristics of their hydrogen bonds, dispersion, and electrostatic (particularly between the positive charge of CO2 and the lone pair of N of alcoholamines) interactions. The extrapolated binding energy from the aug-cc-pVTZ (ATZ) to aug-cc-pVQZ (AQZ) basis set at the CCSD(T)/CBS(MP2+DZ) level was used as the reference for the XC functional comparison. M06-2X produced the optimal agreement if the optimized geometries at MP2/ATZ level were chosen for all the test bound complexes. However, M06-L, ωB97X, and ωB97, and were preferred if the corresponding density functional theory (DFT) optimized geometries were adapted for the benchmark. Simple bimolecular reaction between CO2 and monoethanolamine simulated using polarizable continuum solvation model confirmed that ωB97, ωB97X, and ωB97XD qualitatively reproduced the energetics of MP2 level. The inconsistent performance of the tested XC functionals, observed when using MP2 or DFT optimized geometries, raised concerns regarding using the single-point ab initio correction combined with DFT optimized geometry, particularly for determining the nucleophilic attack by alcoholamines to CO 2.

Original languageEnglish
Pages (from-to)805-812
Number of pages8
JournalInternational Journal of Quantum Chemistry
Volume114
Issue number12
DOIs
Publication statusPublished - 2014 Jun 15

Fingerprint

functionals
Density functional theory
Geometry
density functional theory
geometry
simulation
monoethanolamine (MEA)
Ethanolamine
Solvation
Carbon Monoxide
Binding energy
attack
solvation
Electrostatics
Hydrogen bonds
binding energy
electrostatics
hydrogen bonds
continuums
gradients

Keywords

  • alcoholamines
  • density functional theory

ASJC Scopus subject areas

  • Atomic and Molecular Physics, and Optics
  • Condensed Matter Physics
  • Physical and Theoretical Chemistry

Cite this

Assessment of dispersion-improved exchange-correlation functionals for the simulation of CO2 binding by alcoholamines. / Li, Hsueh Chien; Chai, Jeng Da; Tsai, Ming Kang.

In: International Journal of Quantum Chemistry, Vol. 114, No. 12, 15.06.2014, p. 805-812.

Research output: Contribution to journalArticle

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