TY - JOUR
T1 - Effects of relativity on the Ni - CO, Pd - CO, and Pt - CO bonding mechanism
T2 - A constrained space orbital variation analysis of density functional results
AU - Chung, Sai Cheong
AU - Krüger, Sven
AU - Ruzankin, Sergey Ph
AU - Pacchioni, Gianfranco
AU - Rösch, Notker
N1 - Funding Information:
GP thanks the Alexander von Humboldt Foundation for a research fellowship and SCC the Deutscher Akademischer Austauschdienst for a graduate student fellowship. This work has been supported by the Deutsche Forschungsgemeinschaft, the Volkswagen Foundation and the Fond der Chemischen Indus-trie.
PY - 1996/1/5
Y1 - 1996/1/5
N2 - Using a density functional based constrained space orbital variation technique, we have analyzed the importance of relativistic effects on the various mechanisms which affect the metal - CO bond in Ni, Pd, and Pt monocarbonyls. The bonding is dominated by the π back-donation mechanism which, for Pd and Pt, is considerably reinforced by relativistic effects. The weaker Pd - CO bonding is rationalized by reduced back-donation. The combined effect of relativistic bond length contraction and of the atomic d orbital energies determines the trend in the metal - CO bond strengths. This trend is different from the one found for the coordinatively saturated M(CO)4 tetracarbonyls.
AB - Using a density functional based constrained space orbital variation technique, we have analyzed the importance of relativistic effects on the various mechanisms which affect the metal - CO bond in Ni, Pd, and Pt monocarbonyls. The bonding is dominated by the π back-donation mechanism which, for Pd and Pt, is considerably reinforced by relativistic effects. The weaker Pd - CO bonding is rationalized by reduced back-donation. The combined effect of relativistic bond length contraction and of the atomic d orbital energies determines the trend in the metal - CO bond strengths. This trend is different from the one found for the coordinatively saturated M(CO)4 tetracarbonyls.
UR - http://www.scopus.com/inward/record.url?scp=0030569706&partnerID=8YFLogxK
U2 - 10.1016/0009-2614(95)01273-7
DO - 10.1016/0009-2614(95)01273-7
M3 - Article
AN - SCOPUS:0030569706
SN - 0009-2614
VL - 248
SP - 109
EP - 115
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 1-2
ER -