Rovibrational structure of the Xe–CO complex based on a newthree-dimensional ab initio potential

摘要

The first three-dimensional interaction potential energy surface of the Xe–CO complex is developedusing the single and double excitation coupled cluster theory with noniterative treatment of tripleexcitations. Mixed basis sets, aug-cc-pVQZ for the C and 0 atoms and aug-cc-pVQZ-PP for the Xeatom, including an additional (3s3p2d2flg) set of midbond functions are used. The calculatedsingle point energies at five fixed r_covalues are fitted to an analytic two-dimensional potentialmodel, and further the five model potentials are used to construct the three-dimensional potentialenergy surface by interpolating along (r–r_e).Dynamical calculations with the vibrationallyaveraged potentials are performed to determine the energy levels and the frequencies of variousrovibrational transitions. Our results agree well with the experiment. For example, the IR transitionsof 508 lines are precisely reproduced with only a total rms error of 0.105 cm~(-1).