Relativistic and magnetic Breit effects for the isomerization of Sg(CO)6 and Sg(OC)6

TL;DR

This study uses relativistic quantum calculations to analyze the atomization, isomerization energies, and bond distances of seaborgium hexacarbonyl and its isomer, highlighting the importance of relativistic effects in their properties.

Contribution

First comprehensive relativistic and non-relativistic calculations of seaborgium hexacarbonyl and its isomer, revealing the significant impact of relativistic effects on their energies and structures.

Findings

Relativistic effects decrease isomerization energy by about 1.33 eV.

Predicted bond distances and energies vary significantly between relativistic and non-relativistic calculations.

Both isomers are predicted to exist with distinct energies, complicating experimental identification.

Abstract

Abstract Our ab initio all-electron relativistic Dirac-Fock (DF) calculations for seaborgium hexacarbonyl Sg(CO)6 and seaborgium hexaisocarbonyl Sg(OC)6 predict atomization energies of 68.80 and 64.30 eV. Our Dirac-Fock-Breit-Gaunt (DFBG) calculations for Sg(CO)6 and Sg(OC)6 yield atomization energies of 69.18 and 64.77 eV. However, our calculated non-relativistic (NR) Ae for Sg (CO)6 and Sg(OC)6 are 68.46 and 62.62 eV. The calculated isomerization energies at the DFBG, DF, and NR levels are 4.41,4.50 and 5.83 eV. The contribution of relativity to the Eiso is - ~1.33 eV. The optimized bond distances Sg-C and C-O for octahedral Sg(CO)6 using our DF (NR) calculations are 2.151 ( 2.318 and 1.119 ( 1.114 (ang}). The optimized six Sg-O and C-O bond distances for octahedral Sg(OC)6 at the DF level are equal to 4.897 and 1.108 {ang}. However, the optimized four Sg-O bond distances for the octahedral Sg(OC)6 at the NR level are 5.160 {ang} each, and two Sg-O bonds of 2.721 {ang} each, but all six C-O bonds are 1.108{ang} each. The energies at the DF level of theory for the reaction Sg+6CO to yield Sg (CO)6 and Sg(OC)6 are calculated as -7.30 and -2.80 eV. Moreover, the energies of the reaction at the DFBG level to yield Sg(CO)6 and Sg(OC)6 are very close to those predicted at the DF level of theory of -7.17 and -2.76 eV. However, the NR energies of the above-mentioned reaction are -6.99 and -1.15 eV. The mean bond energies predicted for Sg(CO)6 with our DF, DFBG, and NR calculations are 117.40 , 115.31, and 112.41 kJ/mol, whereas the mean bond energies calculated for the isomer Sg(OC)6 at DF, DFBG and NR levels are 45.03 ,44.39 and 18.49 kJ/mole. The predicted existence of both the isomers with Eiso of ~ 4.50 and ~ 5.80 eV, may cause problems for experimental identification of seaborgium hexacarbonyl.