Large amplitude bending motion in CsOH, studied through ab initio-based three-dimensional potential energy functions |
| |
Authors: | Tsuneo Hirano Valerie Derpmann Per Jensen |
| |
Institution: | a Department of Chemistry, Faculty of Science, Ochanomizu University, 2-1-1 Otsuka, Bunkyo-ku, Tokyo 112-8610, Japan b FB C - Physikalische und Theoretische Chemie, Bergische Universität, D-42097 Wuppertal, Germany c Nanosystem Research Institute, National Institute of Advanced Industrial Science and Technology, 1-1-1 Umezono, Tsukuba, Ibaraki 305-8568, Japan |
| |
Abstract: | 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 re(Cs-O) = 2.3930 Å, re(O-H) = 0.9587 Å, 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 Å, 〈r(O-H)〉0 = 0.9754 Å, 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. |
| |
Keywords: | _method=retrieve& _eid=1-s2 0-S0022285210001657& _mathId=si285 gif& _pii=S0022285210001657& _issn=00222852& _acct=C000053510& _version=1& _userid=1524097& md5=41bedc44a2393fd7ac7a91a52f367fc7')" style="cursor:pointer " alt="Click to view the MathML source" title="Click to view the MathML source"> sciencedirect com/content/image/1-s2 0-S0022285210001657-si285 CsOH" target="_blank">gif"> CsOH Ab initio 3D potential energy surface Molecular constants MORBID ro-vibrationally averaged structure Yamada-Winnewisser quasi-linearity parameter |
本文献已被 ScienceDirect 等数据库收录! |
|