Are High Heats of Atomization for Many Oxides and Fluorides of Z above 37 due to Enhanced Correlation Energy?


  • Christian K. Jørgensen



Heats of atomization Ha (per atom) are compared for for 28 diatomic oxides, 14 diatomic fluorides, 26 solid and 2 polyatomic gaseous oxides, 9 solid and 5 polyatomic gaseous fluorides. There is no universal trend toward lower Ha with increasing Z in a column of the Periodic Table; d-group, post-d-group, and partly filled 4f and 5f shells encourage smaller Ha but barium, lanthanum, lutetium, hafnium, tantalum, (to the largest extent thorium), and uranium show unexpected high Ha. This 'Barium-Thorium Effect' can be rationalized by known facts of correlation energy in atoms and (light) compounds, possibly including indirect relativistic effects due to distorted AO in LCAO.




How to Cite

C. K. Jørgensen, Chimia 1992, 46, 444, DOI: 10.2533/chimia.1992.444.