Interaction energies and structures of the $$\hbox {Li}^{+}{\cdot }(\hbox {CO})_{\hbox {n}}$$ Li + · ( CO ) n (n $$=$$ = 1–3) complexes

Abstract

The bonding and structures of lithium ion carbonyl complexes, $$\hbox {Li}^{+}{\cdot }$$ (CO) $$_{1-3}$$ , were studied at the CCSD and MP2 levels of theories. A linear configuration is formed for the global minimum of the $$\hbox {Li}^{+}{\cdot }$$ CO and $$\hbox {Li}^{+}{\cdot }(\hbox {CO})_{2}$$ complexes with bond dissociation energies of 13.7 and 12.4 kcal $$\hbox {mol}^{-1}$$ , respectively. For the $$\hbox {Li}^{+}{\cdot }(\hbox {CO})_{3}$$ complex, a trigonal planar geometry is formed for the global minimum with a bond dissociation energy of 9.7 kcal $$\hbox {mol}^{-1}$$ . The computed sequential bond dissociation energies of $$\hbox {Li}^{+}{\cdot }(\hbox {CO})_{\mathrm{n}}$$ (n $$=$$ 1–3) complexes agreed with the experimental findings, in which the electrostatic energy plays an important role in the obtained trend. Lithium ion binds with carbon oxides and form three complexes of linear and trigonal planar geometries. These structures affect their sequential bond dissociation energies based on the strength of electrostatic energy contributions. These results match the experimental findings.