Large amplitude bending motion in CsOH, studied through ab initio-based three-dimensional potential energy functions

摘要

The large-amplitude bending motion in CsOH, a 'classical' molecule whose microwave spectrum was first recorded in 1967, has been studied ab initio. The three-dimensional potential energy surface has been calculated at the RCCSD(T)-DK3/[QZP + g ANO-RCC (Cs, O, H)] level of theory and employed in MORBID calculations of the rotation-vibration energies and intensities. The ground electronic state is 1Σ+ with the equilibrium structure r_e(Cs-O) = 2.3930, r_e(O-H) = 0.9587, and ∠_e(Cs-O-H) = 180.0°. The O-H moiety is bound to Cs by an ionic bond and the molecule can be described as Csδ+(OH)δ-. Hence, the bending potential is shallow and gives rise to large-amplitude bending motion. The ro-vibrationally averaged structural parameters, determined as expectation values over MORBID wavefunctions, are 〈r(Cs-O)〉_0 = 2.3987, 〈r(O-H)〉_0 = 0.9754, and 〈∠(Cs-O-H) 〉_0 = 163°. Although the averaged structure in the vibrational ground state is far from being linear, the Yamada-Winnewissi- linearity parameter for CsOH is γ0≈-1.0, the value characteristic for a linear molecule.