Relatives of cyanomethylene: replacement of the divalent carbon by B-, N+, Al-, Si, P+, Ga-, Ge, and As.

The lowest lying singlet and triplet states of HBCN-, HCCN, HNCN+, HAlCN-, HSiCN, HPCN+, HGaCN-, HGeCN, and HAsCN+ were studied using the CCSDT(Q)/CBS//CCSD(T)/aug-cc-pVQZ level of theory. Periodic trends in geometries, singlet-triplet gaps, and barriers to linearity were established and analyzed. The first row increasingly favors the triplet state, with a singlet-triplet gap (ΔEST = Esinglet - Etriplet) of 3.5 kcal mol-1, 11.9 kcal mol-1, and 22.6 kcal mol-1, respectively, for HBCN-, HCCN, and HNCN+. The second row increasing favors the singlet state, with singlet-triplet gaps of -20.4 kcal mol-1 (HAlCN-), -26.6 kcal mol-1 (HSiCN), and -26.8 kcal mol-1 (HPCN+). The third row also favors the singlet state, with singlet-triplet gaps of -26.8 kcal mol-1 (HGaCN-), -33.5 kcal mol-1 (HGeCN), and -33.1 kcal mol-1 (HAsCN+). The HXCN species have larger absolute singlet-triplet energy gaps compared to their parent species XH2 except for the case of X = N+. The effect of the substitution of hydrogen with a cyano group was analyzed with isodesmic bond separation analysis and NBO.