Blocked Localized Wavefunction Analysis of π and σ Bonds in the Metal Carbonyl

Author

Kazuhito Nakashima

Date of Award

6-2008

Degree Name

Master of Science

Department

Chemistry

First Advisor

Dr. Yirong Mo

Second Advisor

Dr. John Miller

Third Advisor

Dr. Ekkehard Sinn

Access Setting

Masters Thesis-Open Access

Abstract

The bonding features in group 10 and 11 metal carbonyls Ni(CO), Pd(CO), Pt(CO), [Cu(CO)]+, [Ag(CO)]+, and [Au(CO)]+ have been studied with BLW method. The carbon monoxide is well known as both a π acceptor and a σ donor. The π back bonding and o bonding are synergistic in these metal carbonyl complexes, because the π donation from the metals polarizes the metals and creates a negative force field as an additional driving force on the σ donation from the carbon end of CO vice versa. The synergistic effect in the metal-carbonyl bonds can be described by decomposing the binding energy into several physically meaningful terms such as charge transfer, polarization, deformation, and Heitler-London energies. Of these energy terms, the charge transfer stabilization energy from the d_x to the antibonding orbital 2π*(CO) and from 5σ(CO) to the empty d_z² is very important to elucidate this synergistic effect.

Recommended Citation

Nakashima, Kazuhito, "Blocked Localized Wavefunction Analysis of π and σ Bonds in the Metal Carbonyl" (2008). Masters Theses. 4324.
https://scholarworks.wmich.edu/masters_theses/4324