Assessment of TD-DFT and LF-DFT for study of d - D transitions in first row transition metal hexaaqua complexes

23Citations
Citations of this article
39Readers
Mendeley users who have this article in their library.
Get full text
This PDF is freely available from an open access repository. It may not have been peer-reviewed.

Abstract

Herein, we present the systematic, comparative computational study of the d - d transitions in a series of first row transition metal hexaaqua complexes, [M(H2O)6]n+ (M2+/3+ = V 2+/3+, Cr2+/3+, Mn2+/3+, Fe2+/3+, Co2+/3+, Ni2+) by the means of Time-dependent Density Functional Theory (TD-DFT) and Ligand Field Density Functional Theory (LF-DFT). Influence of various exchange-correlation (XC) approximations have been studied, and results have been compared to the experimental transition energies, as well as, to the previous high-level ab initio calculations. TD-DFT gives satisfactory results in the cases of d2, d4, and low-spin d6 complexes, but fails in the cases when transitions depend only on the ligand field splitting, and for states with strong character of double excitation. LF-DFT, as a non-empirical approach to the ligand field theory, takes into account in a balanced way both dynamic and non-dynamic correlation effects and hence accurately describes the multiplets of transition metal complexes, even in difficult cases such as sextet-quartet splitting in d5 complexes. Use of the XC functionals designed for the accurate description of the spin-state splitting, e.g., OPBE, OPBE0, or SSB-D, is found to be crucial for proper prediction of the spin-forbidden excitations by LF-DFT. It is shown that LF-DFT is a valuable alternative to both TD-DFT and ab initio methods.

Cite

CITATION STYLE

APA

Vlahović, F., Perić, M., Gruden-Pavlović, M., & Zlatar, M. (2015). Assessment of TD-DFT and LF-DFT for study of d - D transitions in first row transition metal hexaaqua complexes. Journal of Chemical Physics, 142(21). https://doi.org/10.1063/1.4922111

Register to see more suggestions

Mendeley helps you to discover research relevant for your work.

Already have an account?

Save time finding and organizing research with Mendeley

Sign up for free