 |
 |
|
Latouche, C., Palazzetti, F., Skouteris, D. & Barone, V. (2014) High-Accuracy Vibrational Computations for Transition Metal Complexes Including Anharmonic Corrections: Ferrocene, Ruthenocene and Osmocene as test cases. Journal of chemical theory and computation, 10 4565–4573.
Added by: Richard Baschera (2016-09-27 07:35:11) |
| Type de référence: Article DOI: 10.1021/ct5006246 Numéro d'identification (ISBN etc.): 1549-9618 Clé BibTeX: Latouche2014 Voir tous les détails bibliographiques  |
Catégories: HORSIMN Créateurs: Barone, Latouche, Palazzetti, Skouteris Collection: Journal of chemical theory and computation |
Consultations : 1/436
Indice de consultation : 3% Indice de popularité : 0.75% |
| Liens URLs http://dx.doi.org/ ... /10.1021/ct5006246 |
| Résumé |
|
DFT calculations of infrared spectra at harmonic and anharmonic levels of theory have been carried out in order to define a reliable yet feasible strategy to perform accurate computations on metal complexes starting from metallocenes. We present different possibilities to compute with unprecedented accuracy either the ligand vibrations or vibrations where the metal atom is involved or even to obtain the whole spectrum without invoking any scaling factor. Anharmonic calculations employing second order vibrational perturbation theory provide very good results when performed using the B3PW91 hybrid functional associated to an extended basis set and are able to reproduce quantitatively the whole spectrum of ferrocene, including the presence of overtones around 1700 cm-1. Furthermore, our results confirm that B3LYP is the best functional to reproduce ligand vibrations, but, unfortunately, it provides unreliable results for vibrations involving the metal atom. Conversely, the PBE0 functional gives accurate results for metal-ligand vibrational frequencies, but it is quite far from experiment for intra-ligand ones.$backslash$nDFT calculations of infrared spectra at harmonic and anharmonic levels of theory have been carried out in order to define a reliable yet feasible strategy to perform accurate computations on metal complexes starting from metallocenes. We present different possibilities to compute with unprecedented accuracy either the ligand vibrations or vibrations where the metal atom is involved or even to obtain the whole spectrum without invoking any scaling factor. Anharmonic calculations employing second order vibrational perturbation theory provide very good results when performed using the B3PW91 hybrid functional associated to an extended basis set and are able to reproduce quantitatively the whole spectrum of ferrocene, including the presence of overtones around 1700 cm-1. Furthermore, our results confirm that B3LYP is the best functional to reproduce ligand vibrations, but, unfortunately, it provides unreliable results for vibrations involving the metal atom. Conversely, the PBE0 functional gives accurate results for metal-ligand vibrational frequencies, but it is quite far from experiment for intra-ligand ones.
Added by: Richard Baschera |