Analysis of electronic structures and chemical bonding of metal-rich compounds. I. Density functional study of Pt metal, LiPt2, LiPt, and Li2Pt.
First principles density functional theory calculations were carried out for the series of metal-rich compounds, LiPt(2), LiPt, and Li(2)Pt, and elemental Pt for comparison, to probe the bonding picture that captures the essence of their electronic structures. Our analysis shows that the 5d-electron configuration of Pt in these compounds is close to (5d)(10), and the electrons released from the Li atoms in the Li/Pt binary compounds are delocalized among the Pt(0) atoms and Li(+) ions through the interactions of the Pt 5d orbitals of each Pt with the Pt 6s/6p of neighboring Pt atoms and the Li 2s/2p orbitals of neighboring Li atoms. The electron counting schemes best representing the electronic structures of Pt metal, LiPt(2), LiPt and Li(2)Pt are Pt(0) (d(10)), Li(+)[Pt(0) (d(10))](2)(e(-)), Li(+)[Pt(0) (d(10))](e(-)), and (Li(+))(2)[Pt(0) (d(10))](2e(-)), respectively, and hence the Pt atoms of the Li/Pt binary compounds are predicted to exist as partially negative anions.
Lee
Changhoon
C
Department of Chemistry, North Carolina State University, Raleigh, North Carolina 27695-8204, USA.
Whangbo
Myung-Hwan
MH
Köhler
Jürgen
J