Analyses on Molecular Properties of the Diamidinate CrI-CrI Complex by Multireference and DFT Approaches

Gou Tao Huang, Jen-Shiang K. Yu

Research output: Contribution to journalArticlepeer-review

1 Scopus citations

Abstract

The model system of the diamidinate CrI-CrI complex is investigated by wave function theory (WFT) and Kohn-Sham density functional theory (KS-DFT). The multireference perturbation theory (RASPT2) estimates a stabilization energy of ca. 20 kcal mol-1 for the δ bonding. The multiconfiguration pair-density functional theory (MC-PDFT) with the ftPBE functional well predicts the singlet energy curve comparable to the RASPT2 level. For the KS-DFT scheme based on a single determinant, seven functionals including BP86, BLYP, PBE, B3LYP, M06-L, M06, and ωB97X-D are assessed: two types of functionals are classified according to the nature of the restricted and broken symmetry potential energy curves. The broken symmetry scheme with the type I functionals can give good results for the energy curve in agreement with the multireference calculations. In regard to the metal-metal bonding, the restricted KS-DFT calculations performed by all of the seven functionals yield inferior description due to the lack of significant multiconfigurational character. The Mayer bond order, the electron localization function, and electron density predicted by the broken symmetry formalism with the type II functionals are consistent with those obtained with the multireference theory.

Original languageEnglish
Pages (from-to)7803-7813
Number of pages11
JournalThe journal of physical chemistry. A
Volume123
Issue number36
DOIs
StatePublished - 12 Sep 2019

Fingerprint Dive into the research topics of 'Analyses on Molecular Properties of the Diamidinate Cr<sup>I</sup>-Cr<sup>I</sup> Complex by Multireference and DFT Approaches'. Together they form a unique fingerprint.

Cite this