Inexpensive and accurate predictions of optical excitations in transition-metal complexes: the TDDFT/PBE0 route

Abstract

Time-dependent density functional theory (TDDFT) is applied to calculate vertical excitation energies of three representative transition metal complexes. The computational model (PBE0) is obtained by combining the Perdew-Burke-Erzenrhof (PBE) generalized gradient functional with a predetermined amount of exact exchange. Our results show that the TDDFT/ PBE0 model represents a cheap and reliable tool for the computation of optical excitations for transition metal complexes.

TD-DFT Benchmark on Inorganic Pt(II) and Ir(III) Complexes

“…For organic molecules, and especially dyes, one may quote the extensive benchmarks performed by Jacquemin et al in the last years, showing how TD-DFT can provide accurate results for such kinds of compounds after inclusion of some specific corrections (especially accounting for solvent effects). [1][2][3][4][5][6][7][8][9][10][11][12][13][14] However, despite increasing use of the same approach for metal complexes, [15][16][17][18][19][20][21][22][23][24][25][26] or in metal cluster chemistry, [27][28][29][30] benchmarks on those compounds remain difficult to perform, especially due to the requested resources. In any case, some preliminary benchmark study provided encouraging results.…”

Cobalt(ii/iii), nickel(ii) and copper(ii) coordination clusters employing a monoanionic Schiff base ligand: synthetic, topological and computational mechanistic aspects

“…All calculations were performed using the Gaussian 09 program suite. 51 The geometries of all stationary points located on the potential energy surfaces (PESs) were fully optimized without symmetry constraints, employing the 1997 hybrid functional of Perdew, Burke, and Ernzerhof [52][53][54][55][56][57] as implemented in the Gaussian 09 program suite. This functional uses 25% so-called "exact" exchange, i.e.…”

Transient Changes in Molecular Geometries and How to Model Them

“…Different studies on similar transition metal compounds reported satisfactory results using various exchange-correlation functionals, such as B3LYP [99,100] and PBE0 [99,101]. Both are hybrid functionals, but the PBE0 exchange-correlation functional includes 5% more exact Hartree-Fock exchange than B3LYP, in the standard setup.…”