Assessing and applying DFT approaches for geometries and UV-Vis absorption spectra of tetragonal iron(II) complexes

Author(s)

Martins Ramos, Vania ; Campana Severino, Bruno ; Milanez Brugnari, Fernanda ; Conceicao, Livia de Lima ; Rocha, Amanda Santos ; Batista, Ana Paula de Lima

• Document type: Journal article
• Source: THEORETICAL CHEMISTRY ACCOUNTS; v. 143, n. 11, p. 12-pg., 2024-11-01.

Abstract

The performance of density functional theory (DFT)-based calculations combined with different basis set was evaluated on potential iron (II) photosensitizer. BP86-D3(BJ), PBE-D3(BJ), TPSS-D3(BJ), OPBE-D3(BJ), B3LYP-D3(BJ), PBE0-D3(BJ) and TPSSh-D3(BJ) functionals were assessed against X-ray data and the PBE, B3LYP, O3LYP, PBE0, CAM-B3LYP and omega B97X functionals for UV-Vis absorption spectrum. For obtaining the geometries, PBE is a good choice, regardless the basis set size, while OPBE does well only when larger basis set are employed. Regarding the excited states energies, the referred protocol III, EEE,gasTD-DFTRsolvGS-EGS,gasRsolvGS\documentclass[12pt]{minimal} \usepackage{amsmath} \usepackage{wasysym} \usepackage{amsfonts} \usepackage{amssymb} \usepackage{amsbsy} \usepackage{mathrsfs} \usepackage{upgreek} \setlength{\oddsidemargin}{-69pt} \begin{document}$${E}_{\text{EE},\text{gas}}<^>{\text{TD}-\text{DFT}}\left({R}_{\text{solv}}<^>{\text{GS}}\right)-{E}_{\text{GS},\text{gas}}\left({R}_{\text{solv}}<^>{\text{GS}}\right)$$\end{document}, was found to meet the "Pauling Point" criteria, a situation wherein the cancelation of significant errors yields a physically balanced model, allowing an affordable and reliable way to understand their excited state's electronic structure. Specifically, TD-DFT calculations using def2-TZVP basis set combined with B3LYP or CAM-B3LYP functionals can be recommended to treat the excited states of the explored iron (II) complex. The study additionally looks at the molecular and electronic structures of a series of similar complexes, collecting understanding to help tune their properties and of related systems as photosensitizers. (AU)

• FAPESP's process: 24/01971-4 - Computacional Design of First-Row Transition Metal Complexes Based Photosensitizers.
• Grantee: Vania Martins Ramos
• Support Opportunities: Scholarships in Brazil - Doctorate
• FAPESP's process: 23/18324-9 - The Influence of Different Ligands on the Electronic Structure of the Fe(HMTI)(CN)2 Photosensitizer: A Computational Approach
• Grantee: Fernanda Milanez Brugnari
• Support Opportunities: Scholarships in Brazil - Scientific Initiation
• FAPESP's process: 22/12043-5 - Structure and spectroscopy of first row transition metal complexes: a computacional approach
• Grantee: Ana Paula de Lima Batista
• Support Opportunities: Regular Research Grants
• FAPESP's process: 21/00675-4 - Tying up materials for electrochemical energy storage and catalysis
• Grantee: Roberto Manuel Torresi
• Support Opportunities: Research Projects - Thematic Grants