Towards J/mol Accuracy for the Cohesive Energy of Solid Argon.
The cohesive energies of argon in its cubic and hexagonal closed packed structures are computed with an unprecedented accuracy of about 5 J mol(-1) (corresponding to 0.05 % of the total cohesive energy). The same relative accuracy with respect to experimental data is also found for the face-centered cubic lattice constant deviating by ca. 0.003 Å. This level of accuracy was enabled by using high-level theoretical, wave-function-based methods within a many-body decomposition of the interaction energy. Static contributions of two-, three-, and four-body fragments of the crystal are all individually converged to sub-J mol(-1) accuracy and complemented by harmonic and anharmonic vibrational corrections. Computational chemistry is thus achieving or even surpassing experimental accuracy for the solid-state rare gases.
Centre for Theoretical Chemistry and Physics, The New Zealand Institute for Advanced Study, Massey University Auckland, Private Bag 102904, 0632, Auckland, New Zealand. p.a.schwerdtfeger@massey.ac.nz.
Peter
P
Schwerdtfeger
Fachbereich Chemie, Philipps-Universität Marburg, Hans-Meerwein-Str. 4, 35032, Marburg, Germany.
Ralf
0000-0002-6759-8559
R
Tonner
Instituto de Química, Universidad de Antioquia, AA 1126, Medellín, Colombia.
Gloria E
GE
Moyano
Centre for Theoretical Chemistry and Physics, Institute for Natural and Mathematical Sciences, Massey University Auckland, Private Bag 102904, 0632, Auckland, New Zealand.
Elke
E
Pahl
accuracy; argon; cohesive energy; many-body expansion; solid-state properties