Small-Basis Set Density-Functional Theory Methods Corrected with Atom-Centered Potentials

doi:10.1021/acs.jctc.2c00036

Small-Basis Set Density-Functional Theory Methods Corrected with Atom-Centered Potentials

2022-04-12

12

PRE

AI

V

Viki Kumar Prasad

A

Alberto Otero‐de‐la‐Roza *

G

Gino A. DiLabio *

DOI：10.1021/acs.jctc.2c00036

Original

Original request for help

Save

Abstract

En 中文

Density functional theory (DFT) is currently the most popular method formodeling noncovalent interactions and thermochemistry. The accurate calculation of noncovalentinteraction energies, reaction energies, and barrier heights requires choosing an appropriatefunctional and, typically, a relatively large basis set. Deficiencies of the density-functionalapproximation and the use of a limited basis set are the leading sources of error in the calculationof noncovalent and thermochemical properties in molecular systems. In this article, we presentthree new DFT methods based on the BLYP, M06-2X, and CAM-B3LYP functionals incombination with the 6-31G*basis set and corrected with atom-centered potentials (ACPs). ACPs are one-electron potentials thathave the same form as effective-core potentials, except they do not replace any electrons. The ACPs developed in this work are usedto generate energy corrections to the underlying DFT/basis-set method such that the errors in predicted chemical properties areminimized while maintaining the low computational cost of the parent methods. ACPs were developed for the elements H, B, C, N,O, F, Si, P, S, and Cl. The ACP parameters were determined using an extensive training set of 118655 data points, mostly ofcomplete basis set coupled-cluster level quality. The target molecular properties for the ACP-corrected methods include noncovalentinteraction energies, molecular conformational energies, reaction energies, barrier heights, and bond separation energies. The ACPswere testedfirst on the training set and then on a validation set of 42567 additional data points. We show that the ACP-correctedmethods can predict the target molecular properties with accuracy close to complete basis set wavefunction theory methods, but at acomputational cost of double-zeta DFT methods. This makes the new BLYP/6-31G*-ACP, M06-2X/6-31G*-ACP, and CAM-B3LYP/6-31G*-ACP methods uniquely suited to the calculation of noncovalent, thermochemical, and kinetic properties in large molecular systems

Keywords:

MAIN-GROUP THERMOCHEMISTRY

QUANTUM-CHEMICAL METHODS

BENCHMARK INTERACTION ENERGIES

DER-WAALS INTERACTIONS

AB-INITIO METHODS

NONCOVALENT INTERACTIONS

BARRIER HEIGHTS

WAVE-FUNCTION

CONFORMATIONAL ENERGIES

WATER CLUSTERS

Small-Basis Set Density-Functional Theory Methods Corrected with Atom-Centered Potentials

Abstract

Journal

Organization