Structures and Thermochemistry of the Alkali Metal Monoxide Anions, Monoxide Radicals, and Hydroxides

Abstract

The geometries, enthalpies of formation (DeltaH(o)(f)), separations of electronic states, electron affinities, gas-phase acidities, and bond dissociation energies associated with the alkali metal monoxide anions (MO(-)), monoxide radicals (MO(*)), and hydroxides (MOH) (M = Li, Na, and K) have been investigated using single-reference and multireference variants of the WnC procedures. Our best estimates of the DeltaH(o)(f) values for the ground states at 298 K are as follows: 8.5 ((3)Pi LiO(-)), 48.5 ((2)Pi LiO(*)), -243.4 ((1)Sigma(+) LiOH), 34.2 ((3)Pi NaO(-)), 86.4 ((2)Pi NaO(*)), -190.8 ((1)Sigma(+) NaOH), 15.1 ((1)Sigma(+) KO(-)), 55.9 ((2)Sigma(+) KO(*)), and -227.0 ((1)Sigma(+) KOH) kJ mol(-1). While the LiO(*) and NaO(*) radicals have (2)Pi ground states, for KO(*), the (2)Sigma(+) and (2)Pi electronic states lie very close in energy, with our best estimate being a preference for the (2)Sigma(+) state by 1.1 kJ mol(-1) at 0 K. In a similar manner, the ground state for MO(-) changes from (3)Pi for LiO(-) and NaO(-) to (1)Sigma(+) for KO(-). The (1)Sigma(+) state of KO(-) is indicated by the calculated T(1) diagnostic and the SCF contribution to the total atomization energy to have a significant degree of multireference character. This leads to a difference of more than 100 kJ mol(-1) between the single-reference W2C and multireference W2C-CAS-ACPF and W2C-CAS-AQCC estimates for the (1)Sigma(+) DeltaH(o)(f) for KO(-).