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

Autor(es)

Mendes, Rodrigo Araujo ^[1] ; Andrade Haiduke, Roberto Luiz ^[1]

Afiliação do(s) autor(es)

^[1] Univ Sao Paulo, Inst Quim Sao Carlos, Dept Quim & Fis Mol, CP 780, BR-13560970 Sao Carlos, SP - Brazil

• Tipo de documento: Artigo Científico
• Fonte: THEORETICAL CHEMISTRY ACCOUNTS; v. 140, n. 11 NOV 2021.
• Citações Web of Science: 0

Resumo

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)

• Processo FAPESP: 13/07375-0 - CeMEAI - Centro de Ciências Matemáticas Aplicadas à Indústria
• Beneficiário: Francisco Louzada Neto
• Modalidade de apoio: Auxílio à Pesquisa - Centros de Pesquisa, Inovação e Difusão - CEPIDs
• Processo FAPESP: 14/23714-1 - Cálculos relativísticos de estrutura eletrônica para avaliação de novos conjuntos de funções de base sem prolapso variacional
• Beneficiário: Roberto Luiz Andrade Haiduke
• Modalidade de apoio: Auxílio à Pesquisa - Regular