Issue 6, 2023

On the accuracy of orbital based multi-level approaches for closed-shell transition metal chemistry

Abstract

In this work, we investigate the accuracy of the local molecular orbital molecular orbital (LMOMO) scheme and projection-based wave function-in-density functional theory (WF-in-DFT) embedding for the prediction of reaction energies and barriers of typical reactions involving transition metals. To analyze the dependence of the accuracy on the system partitioning, we apply a manual orbital selection for LMOMO as well as the so-called direct orbital selection (DOS) for both approaches. We benchmark these methods on 30 closed shell reactions involving 16 different transition metals. This allows us to devise guidelines for the manual selection as well as settings for the DOS that provide accurate results within an error of 2 kcal mol−1 compared to local coupled cluster. To reach this accuracy, on average 55% of the occupied orbitals have to be correlated with coupled cluster for the current test set. Furthermore, we find that LMOMO gives more reliable relative energies for small embedded regions than WF-in-DFT embedding.

Graphical abstract: On the accuracy of orbital based multi-level approaches for closed-shell transition metal chemistry

Supplementary files

Article information

Article type
Paper
Submitted
28 အောက် 2022
Accepted
09 ဇန် 2023
First published
09 ဇန် 2023
This article is Open Access
Creative Commons BY-NC license

Phys. Chem. Chem. Phys., 2023,25, 4635-4648

On the accuracy of orbital based multi-level approaches for closed-shell transition metal chemistry

Z. Amanollahi, L. Lampe, M. Bensberg, J. Neugebauer and M. Feldt, Phys. Chem. Chem. Phys., 2023, 25, 4635 DOI: 10.1039/D2CP05056K

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