Geometries and adiabatic excitation energies of the low-lying valence states of CNC, C2N, N3 and NCO studied with the electron-attached and ionized equation-of-motion coupled-cluster methodologies

Abstract

The full and active-space variants of the electron-attached (EA) equation-of-motion (EOM) coupled-cluster (CC) method with up to three-particle–two-hole (3p–2h) excitations in the electron-attaching operator Rμ(N+1) that use the CC singles and doubles (CCSD) approach to obtain the ground state of the reference N-electron closed-shell system, abbreviated as EA-EOMCCSD(3p–2h), and their ionized (IP) counterparts with up to three-hole–two-particle (3h–2p) excitations in the ionizing operator Rμ(N−1), abbreviated as IP-EOMCCSD(3h–2p), are used to optimize the geometries of the ground and low-lying excited states of four open-shell molecules, CNC, C2N, NCO and N3, and determine the corresponding adiabatic excitation energies. The full and active-space EA-EOMCCSD(3p–2h) results for the CNC and C2N molecules, obtained with the correlation-consistent basis sets as large as cc-pVTZ and cc-pVQZ, respectively, are compared with one another, with the corresponding EA-EOMCCSD(2p–1h) calculations, with the previously generated small basis set EA-EOMCC and symmetry-adapted-cluster configuration-interaction (SAC-CI-SDT-R/PS) data, and, wherever possible, with experiment. The analogous comparison of the full and active-space IP-EOMCCSD(3h–2p) results with the IP-EOMCCSD(2h–1p), SAC-CI-SDT-R/PS and experimental data is performed for the NCO and N3 molecules. It is shown that the active-space EA-EOMCCSD(3p–2h) and IP-EOMCCSD(3h–2p) approaches using small numbers of active orbitals, which have computational costs that are of the order of the CCSD calculations, provide excitation energies and optimized geometries that are in excellent agreement with the results of the significantly more expensive parent EA-EOMCCSD(3p–2h) and IP-EOMCCSD(3h–2p) calculations, independent of the basis set. It is also demonstrated that the basic EA-EOMCCSD(2p–1h) and IP-EOMCCSD(2h–1p) methods, while generally inadequate for a reliable description of the excitation energies, describe the geometries in a reasonable manner, including excited states dominated by two-electron transitions. Although the full and active-space EA-EOMCCSD(3p–2h) calculations for the most challenging CNC and C2N molecules improve the EA-EOMCCSD(2p–1h) excitation energies, some differences with the available experimental data remain in spite of the use of larger correlation-consistent basis sets and complete basis set extrapolations.