Concordant Mode Approach (CMA): Vibrational Analysis of New and Upgraded Intermolecular Benchmarks for Noncovalent Bonding

Résumé fourni par la source

High Resolution Image Download MS PowerPoint Slide The Concordant Mode Approach (CMA) is a novel method that offers tremendous potential for increasing the system size and the level of theory attainable in quantum chemical computations of molecular vibrational frequencies. To investigate the extension of CMA to intermolecular vibrations, computations with coupled cluster singles and doubles with perturbative triples theory [CCSD(T)] using two augmented correlation-consistent polarized-valence triple-ζ basis sets (aug-cc-pVTZ or h-aug-cc-pVTZ) were performed on 17 prototypical loosely bound complexes of hydrogen-bonded, dispersion, and mixed character. These Level A results provide new and upgraded benchmarks for noncovalent bonding and a severe test for CMA vibrational analyses. The Level A target frequencies were recovered remarkably well using second-order Møller–Plesset perturbation theory (MP2) with h-aug-cc-pVTZ for generating the underlying (Level B) normal modes of the CMA scheme. Employing this Level B within the lowest-rung CMA-0A method reproduces the 435 benchmark frequencies with a mean absolute error (MAE) of 0.23 cm –1 and a corresponding standard deviation (σ) of 0.84 cm –1; strikingly, the corresponding subset of 106 interfragment frequencies exhibits MAE = 0.34 cm –1 and σ = 0.90 cm –1 . Subsequent application of the higher-rung CMA-2A scheme eliminates all outliers and reduces the overall MAE to a minuscule 0.08 cm –1 with the inclusion of only 3.0% of the off-diagonal couplings not accounted for by CMA-0A. Accordingly, the highly efficient CMA methodology proves to be robust even for vibrations on flat potential energy surfaces.

Ce résumé expose les affirmations des auteurs. BNTIC ne l’interprète pas comme une validation indépendante des résultats.