TY - JOUR
T1 - Relativistic effects in bonding and isomerization energy of the superheavy roentgenium ( 111Rg) cyanide
AU - Muñoz-Castro, Alvaro
AU - Carey, Desmond Mac Leod
AU - Arratia-Perez, Ramiro
AU - Malli, Gulzari L.
N1 - Funding Information:
The authors thank the financial support of FONDECYT Grants 1100283 , 11100027 , 1110758 and 7100005 , and PROJECT MILLENNIUM No. P07-006-F. This research used in part resources of the National Energy Research Scientific Computing Center (NERSC), which is supported by the Office of Science of the US Department of Energy under Contract No. DE-AC03-76SF00098, and WestGrid computing facility at Simon Fraser University, Canada.
PY - 2012/5/30
Y1 - 2012/5/30
N2 - The cyanide and isocyanides of the superheavy roentgenium ( 111Rg) element are investigated using relativistic 4-component Dirac-Fock (DF) and 2-component Density-Functional Theory (DFT) with ZORA Hamiltonian. The relativistic effects in bonding and energetics allow us to conclude that these complexes could be synthesized in a linear conformation with a preference for the RgCN isomer. The relativistic effects (RE) lead to an increase in the covalent character of the Rg(I)-ligand interaction, resulting in a higher charge transfer from the ligand to the metal by an enhanced acceptor character of Rg(I), mainly due to the relativistic stabilization of the 7s shell. The inclusion of the spin-orbit interaction modifies the bonding picture leading to a decrease of about 40 kcal/mol in the bonding interaction in both isomers. In conclusion, our calculations at several levels of theory suggest that it is possible to develop an exotic chemistry of complexes involving Rg(I) and the CN - ligand.
AB - The cyanide and isocyanides of the superheavy roentgenium ( 111Rg) element are investigated using relativistic 4-component Dirac-Fock (DF) and 2-component Density-Functional Theory (DFT) with ZORA Hamiltonian. The relativistic effects in bonding and energetics allow us to conclude that these complexes could be synthesized in a linear conformation with a preference for the RgCN isomer. The relativistic effects (RE) lead to an increase in the covalent character of the Rg(I)-ligand interaction, resulting in a higher charge transfer from the ligand to the metal by an enhanced acceptor character of Rg(I), mainly due to the relativistic stabilization of the 7s shell. The inclusion of the spin-orbit interaction modifies the bonding picture leading to a decrease of about 40 kcal/mol in the bonding interaction in both isomers. In conclusion, our calculations at several levels of theory suggest that it is possible to develop an exotic chemistry of complexes involving Rg(I) and the CN - ligand.
KW - Dirac-Fock
KW - Isomerization energy
KW - Roentgenium cyanide and isocyanides
KW - Super-heavy elements
UR - http://www.scopus.com/inward/record.url?scp=84860455015&partnerID=8YFLogxK
U2 - 10.1016/j.poly.2012.03.032
DO - 10.1016/j.poly.2012.03.032
M3 - Article
AN - SCOPUS:84860455015
SN - 0277-5387
VL - 39
SP - 113
EP - 117
JO - Polyhedron
JF - Polyhedron
IS - 1
ER -