Theoretical study on germanium cyanide radical GeCN and its ions

A detailed theoretical study is performed on the hitherto unknown germanium cyanide radical and its ions. The ²∏ state GeCN lies 5.0 kcal/mol lower than the ²∏ state GeNC at the coupled-cluster theory including single and double excitations and perturbative inclusion of triple excitations [CCSD(T)]/ 6-311++G (3df) //quadratic configuration interaction with single and double excitations (QCISD)/ 6-311G (d) +zero-point vibrational energy (ZPVE) level. For interconversion between them, two electronic state pathways A′2 and A″2 are located, with the latter being 0.7 kcal/mol more favorable than the former. On the A″2 path, the GeCN→GeNC and GeNC→GeCN conversion barriers are 14.5 and 9.5 kcal/mol, respectively. The detailed singlet and triplet potential-energy surfaces of both the cationic and anionic GeCN species are also investigated. On the ground-state electronic hypersurface, singlet GeNC+ is 4.6 kcal/mol more stable than singlet GeCN+, whereas triplet GeNC- is 10.0 kcal/mol less stable than triplet GeCN-. The relative energy difference between the GeCN0,± and GeNC0,± can be well correlated with the number of vacant orbitals on the Ge atom. The stability of the neutral and ionic CGeN and cyclic cGeCN is also discussed. The predicted structures, spectroscopies, ionization, and affinity energies as well as the Renner-Teller properties are expected to provide reliable estimates for future characterization of the potential GeCN and GeNC radicals as well as their ionic counterparts both in the laboratory and in the interstellar space.