Prediction of the reduction potential in transition-metal containing complexes: How expensive? For what accuracy?

Abstract

Accurate computationally derived reduction potentials are important for catalyst design. In this contribution, relatively inexpensive density functional theory methods are evaluated for computing reduction potentials of a wide variety of organic, inorganic, and organometallic complexes. Astonishingly, SCRF single points on B3LYP optimized geometries with a reasonably small basis set/ECP combination works quite well--B3LYP with the BS1 [modified-LANL2DZ basis set/ECP (effective core potential) for metals, LANL2DZ(d,p) basis set/LANL2DZ ECP for heavy nonmetals (Si, P, S, Cl, and Br), and 6-31G(d') for other elements (H, C, N, O, and F)] and implicit PCM solvation models, SMD (solvation model based on density) or IEFPCM (integral equation formalism polarizable continuum model with Bondi atomic radii and α = 1.1 reaction field correction factor). The IEFPCM-Bondi-B3LYP/BS1 methodology was found to be one of the least expensive and most accurate protocols, among six different density functionals tested (BP86, PBEPBE, B3LYP, B3P86, PBE0, and M06) with thirteen different basis sets (Pople split-valence basis sets, correlation consistent basis sets, or Los Alamos National Laboratory ECP/basis sets) and four solvation models (SMD, IEFPCM, IPCM, and CPCM). The MAD (mean absolute deviation) values of SCRF-B3LYP/BS1 of 49 studied species were 0.263 V for SMD and 0.233 V for IEFPCM-Bondi; and the linear correlations had respectable R2 values (R2 = 0.94 for SMD and R2 = 0.93 for IEFPCM-Bondi). These methodologies demonstrate relatively reliable, convenient, and time-saving functional/basis set/solvation model combinations in computing the reduction potentials of transition metal complexes with moderate accuracy. © 2017 Wiley Periodicals, Inc.

Publication Title

Journal of Computational Chemistry

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