Electronic spectroscopy of carbon chains (C2n+1, n=7-10) of astrophysical importance. I. Quantum chemistry

摘要

Carbon chains have been predicted to be potential carriers of diffuse interstellar band features in astrophysical observations. Motivated by numerous predictions, we set out to carry out extensive ab initio quantum chemistry calculations to establish the ground and excited electronic potential energy surfaces and their coupling surfaces for carbon chains containing an odd number of carbon atoms (C2n+1, n = 7-10). Vibronic coupling models are established with the aid of the calculated electronic energies to investigate nuclear dynamics from first principles. The latter are reported in Ghosh et al. [J. Chem. Phys. 151, 054304 (2019)]. The mentioned carbon chains possess a linear cumulenic structure at the equilibrium minimum of their electronic ground state, and an electronic excited state of the (1)Sigma(+)(u) term appears to be extremely bright optically and absorbs in the visible region of the electromagnetic spectrum. Vertical excitation energy of this state decreases and transition dipole moment increases, and as a result, the oscillator strength of this state linearly increases with an increase of the chain length. There are states belonging to (1)Pi(g), (1)Pi(u), (1)Sigma(+)(g), (1)Delta(g), and (1)Delta(u) terms, in the immediate vicinity of the (1)Sigma(+)(u) state, which are optically dark but can gain intensity through vibronic coupling with the optically bright (1)Sigma(+)(u) state. Construction of a coupling scheme considering the Renner-Teller coupling within the degenerate Pi states and pseudo-Renner-Teller coupling between the Renner-Teller split component states as well as with the nondegenerate Sigma states is another motivation of this work. The coupled-state Hamiltonian is constructed in a diabatic electronic basis in terms of the dimensionless normal coordinates of the vibrational modes of the carbon chains. Both Renner-Teller and pseudo-Renner-Teller types of couplings are included in the Hamiltonian. The theoretical results are discussed in rela