Ill-advised self-interaction contribution in modelling anionic attack along a reaction path. (17th April 2016)

• Record Type: Journal Article
• Authors: Lamine, Walid; Boughdiri, Salima; Christ, Lorraine; Morell, Christophe; Chermette, Henry
• Is Part Of: Molecular physics. Volume 114:Number 7/8(2016)
• Page Start: 1066
• Page End: 1075
• Publication Date: 2016-04-17
• Subjects: DFT -- self-interaction -- reaction path -- anion -- free iodide; Molecules -- Periodicals; Chemistry, Physical and theoretical -- Periodicals; Molécules -- Périodiques; Chimie physique et théorique -- Périodiques; 539.6.05
• DOI: 10.1080/00268976.2015.1134828
• Languages: English
• ISSNs: 0026-8976

Abstract

GRAPHICAL ABSTRACT: ABSTRACT: It is shown that modelling a catalytic reaction involving an atomic anion, such as iodide, may lead to unrealistic reaction paths because of the underestimation of the anion energy. The self-interaction error, at the origin of this feature is enhanced by the fact that electronic delocalisation, usually overestimated in DFT calculations, cannot occur in a single atom. The quantification of this error is approached by a linear transit calculation, from a transition state towards separate fragments. This is an efficient way to correct this error for GGA functionals. Interestingly the self-interaction error is shown to be less dependent of the Hartree–Fock exchange amount in hybrid functionals than expected. Unexpectedly, no significant improvement with long-range corrected functionals is obtained.