Theoretical insight into electronic spectra of carbon chain carbenes H2Cn (n = 3-10)

Ground-state geometries of carbenes H2Cn (n = 3-10) have been fully optimized with the C2ν-symmetry constraint at the density functional theory and restricted-spin coupled-cluster single-double plus perturbative triple excitation levels of theory, respectively. Comparison of structures corresponding to the X(1)A1 and B(1)B1 electronic states has been made by the complete active space self-consistent field calculations. Parity alternation effect on various properties of the ground-state geometries has been discovered in the present study, which generally gives illustration for the relative stabilities of the titled carbon chains. Further calculations on their electronic spectra have been carried out by means of the complete active space second-order perturbation theory method along with the cc-pVTZ basis set. It is found that the vertical excitation energies of the dipole-allowed B(1)B1 ← X(1)A1 transition in the gas phase are 2.28, 4.75, 1.69, 3.66, 1.30, 2.94, 1.12, and 2.49 eV, respectively, which agree very well with the available experimental result for H2C3 (2.27 eV). In addition, the vertical excitation energies for both transitions B(1)B1 ← X(1)A1 and A(1)A2 ← X(1)A1 are found to obey a nonlinear ΔE-n relationship as a function of chain size by performing curves fitting.