Structures and heats of formation of simple alkali metal compounds: hydrides, chlorides, fluorides, hydroxides, and oxides for Li, Na, and K.
Geometry parameters, frequencies, heats of formation, and bond dissociation energies are predicted for simple alkali metal compounds (hydrides, chlorides, fluorides, hydroxides and oxides) of Li, Na, and K from coupled cluster theory [CCSD(T)] calculations including core-valence correlation with the aug-cc-pwCVnZ basis set (n = D, T, Q, and 5). To accurately calculate the heats of formation, the following additional correction were included: scalar relativistic effects, atomic spin-orbit effects, and vibrational zero-point energies. For calibration purposes, the properties of some of the lithium compounds were predicted with iterative triple and quadruple excitations via CCSDT and CCSDTQ. The calculated geometry parameters, frequencies, heats of formation, and bond dissociation energies were compared with all available experimental measurements and are in excellent agreement with high-quality experimental data. High-level calculations are required to correctly predict that K(2)O is linear and that the ground state of KO is (2)Sigma(+), not (2)Pi, as in LiO and NaO. This reliable and consistent set of calculated thermodynamic data is appropriate for use in combustion and atmospheric simulations.
Vasiliu
Monica
M
Chemistry Department, Shelby Hall, The University of Alabama, Box 870336, Tuscaloosa, Alabama 35487-0336, USA.
Li
Shenggang
S
Peterson
Kirk A
KA
Feller
David
D
Gole
James L
JL
Dixon
David A
DA