PNNL

Abstract

Cyclobutane-1,2,3,4-tetraone has been both predicted and found to have a triplet ground state, in which a b2g MO and an a2u MO is each singly occupied. In contrast, (CO)5 and (CO)6 have each been predicted to have a singlet ground state. This prediction has been tested by generating the (CO)5 - and (CO)6 - anions in the gas-phase by electrospray vaporization of solutions of, respectively, the croconate (CO)52- and rhodizonate (CO)62- dianions. The negative ion photoelectron (NIPE) spectra of the (CO)5•- radical anion give electron affinity (EA) = 3.830 eV and a singlet ground state for (CO)5, with the triplet higher in energy by 0.850 eV (19.6 kcal/mol). The NIPE spectra of the (CO)6•- radical anion give EA = 3.785 eV and a singlet ground state for (CO)6, with the triplet higher in energy by 0.915 eV (21.1 kcal/mol). (RO)CCSD(T)/aug-cc-pVTZ//(U)B3LYP/6-311+G(2df) calculations give EA values that are only ca. 1 kcal/mol lower than those measured and EST values that are only 2 - 3 kcal/mol higher than those obtained from the NIPE spectra. Thus, the calculations support the interpretations of the NIPE spectra and the finding, based on the spectra, that (CO)5 and (CO)6 both have a singlet ground state.