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(Reference retrieved automatically from Web of Science through information on FAPESP grant and its corresponding number as mentioned in the publication by the authors.)

Performance of new exchange-correlation functionals in providing vertical excitation energies of metal complexes

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Author(s):
Mendes, Rodrigo Araujo [1] ; Andrade Haiduke, Roberto Luiz [1]
Total Authors: 2
Affiliation:
[1] Univ Sao Paulo, Inst Quim Sao Carlos, Dept Quim & Fis Mol, CP 780, BR-13560970 Sao Carlos, SP - Brazil
Total Affiliations: 1
Document type: Journal article
Source: THEORETICAL CHEMISTRY ACCOUNTS; v. 140, n. 11 NOV 2021.
Web of Science Citations: 0
Abstract

The performance of Hartree-Fock and twenty-three exchange-correlation functionals from Density Functional Theory was evaluated by means of experimental values of vertical excitation energies in metal complexes (tetraoxos, carbonyls, and halides) by using augmented basis sets of two different sizes, double- and triple-zeta. The analysis is carried out in terms of linear correlation parameters, that is, coefficients of determination and slope errors. In general, the results present only a small dependency with the basis set size. Range-separated hybrids (RSHs), mainly by LC-PBEPBE and LC-QTP, show the best performance for tetraoxo complexes. In addition, all methods provide poor results for carbonyls, where functionals from Local Density Approximation and Generalized Gradient Approximation (GGA) are better, followed by hybrids and RSHs. Moreover, hybrids, hybrid meta-GGAs (except for M06-HF), and mainly RSHs are more successful for halide complexes. Finally, considering all systems together, the functionals that provide the largest coefficients of determination (R-2 >= 0.98) along with the smallest slope errors (Error(alpha) < 0.08) are the RSHs, except for CAM-QTP-00. This comparative investigation should contribute to future studies regarding the general analysis of optical properties in metal complexes. (AU)

FAPESP's process: 13/07375-0 - CeMEAI - Center for Mathematical Sciences Applied to Industry
Grantee:Francisco Louzada Neto
Support Opportunities: Research Grants - Research, Innovation and Dissemination Centers - RIDC
FAPESP's process: 14/23714-1 - Electronic structure relativistic calculations for evaluation of new prolapse-free basis sets
Grantee:Roberto Luiz Andrade Haiduke
Support Opportunities: Regular Research Grants