PNNL

Abstract

Atomization energies at 0 K and heats of formation at 0 and 298 K are predicted for XeF3?, XeF3?, XeF5?, XeF7?, and XeF8 from coupled cluster theory (CCSD(T)) calculations with effective core potential correlation-consistent basis sets for Xe and including correlation of the nearest core electrons. Additional corrections are included to achieve near chemical accuracy of ±1 kcal/mol. Vibrational zero point energies were computed at the MP2 level of theory. Unlike the other neutral xenon fluorides, XeF8 is predicted to be thermodynamically unstable with respect to loss of F2 with the reaction calculated to be exothermic by 22.3 kcal/mol at 0 K. XeF7? is also predicted to be thermodynamically unstable with respect to the loss of F2 by 24.1 kcal/mol at 0 K. For XeF3?, XeF5?, XeF3?, XeF5? and XeF7?, the reactions for loss of F2 are endothermic by 14.8, 37.8, 38.2, 59.6, and 31.9 kcal/mol at 0 K, respectively. The F? affinities of Xe, XeF2, XeF4, and XeF6 are predicted to be 165.1, 155.3, 172.7, and 132.5 kcal/mol, and the corresponding F? affinities are 6.3, 19.9, 59.1, and 75.0 kcal/mol at 0 K, respectively.