A theoretical investigation of the energetics and spectroscopic properties of the gas-phase linear proton-bound cation-molecule complexes, XCH(+)-N2 (X = O, S).

The structural features, spectroscopic properties, and interaction energies of the linear proton-bound complexes of OCH(+) and its sulfur analog SCH(+) with N2 were investigated using the high-level ab initio methods MP2 and CCSD(T) as well as density functional theory with the aug-cc-pVXZ (X = D, T) basis sets. The rotational constants along with the vibrational frequencies of the cation-molecule complexes are reported here. A comparison of the interaction energies of the OCH(+)-N2 and SCH(+)-N2 complexes with those of the OCH(+)-CO and OCH(+)-OC complexes was also performed. The energies of all the complexes were determined at the complete basis set (CBS) limit. CS shows higher proton affinity at the C site than CO does, so the complex OCH(+)-N2 is relatively strongly bound and has a higher interaction energy than the SCH(+)-N2 complex. Symmetry-adapted perturbation theory (SAPT) was used to decompose the total interaction energies of the complexes into the attractive electrostatic interaction energy (E elst), induction energy (E ind), dispersion energy (E disp), and repulsive exchange energy (E exch). We found that the ratio of E ind to E disp is large for these linear proton-bound complexes, meaning that inductive effects are favored in these complexes. The bonding characteristics of the linear complexes were elucidated using natural bond orbital (NBO) theory. NBO analysis showed that the attractive interaction is caused by NBO charge transfer from the lone pair on N to the σ*(C-H) antibonding orbital in XCH(+)-N2 (X = O, S). The quantum theory of atoms in molecules (QTAIM) was used to analyze the strengths of the various bonds within and between the cation and molecule in each of these proton-bound complexes in terms of the electron density at bond critical points (BCP). Graphical Abstract Linear proton-bound complexes of OCH(+)-N2 and SCH(+)-N2. In these complexes, inductive effect is favored over dispersive effect. The attractive interaction is the NBO charge transfer from N-lone pair of N2 to CH σ* antibonding orbital of XCH(+) (X = O, S).