Feng Eryin, Zhang Yu, Wang Zhongquan, Niu Mei, Cui Zhifeng
Department of Physics, Anhui Normal University, Wuhu 241000, People's Republic of China.
J Chem Phys. 2009 Mar 28;130(12):124311. doi: 10.1063/1.3100754.
The first three-dimensional interaction potential energy surface of the Xe-CO complex is developed using the single and double excitation coupled cluster theory with noniterative treatment of triple excitations. Mixed basis sets, aug-cc-pVQZ for the C and O atoms and aug-cc-pVQZ-PP for the Xe atom, including an additional (3s3p2d2f1g) set of midbond functions are used. The calculated single point energies at five fixed r(co) values are fitted to an analytic two-dimensional potential model, and further the five model potentials are used to construct the three-dimensional potential energy surface by interpolating along (r-r(e)). Dynamical calculations with the vibrationally averaged potentials are performed to determine the energy levels and the frequencies of various rovibrational transitions. Our results agree well with the experiment. For example, the IR transitions of 508 lines are precisely reproduced with only a total rms error of 0.105 cm(-1).
利用单双激发耦合簇理论并对三激发进行非迭代处理，构建了Xe - CO络合物的首个三维相互作用势能面。使用混合基组，C和O原子采用aug - cc - pVQZ，Xe原子采用aug - cc - pVQZ - PP，其中包括一组额外的（3s3p2d2f1g）中键函数。将在五个固定r(co)值处计算的单点能量拟合到一个解析二维势模型中，进而通过沿（r - r(e)）进行插值，利用这五个模型势构建三维势能面。利用振动平均势进行动力学计算，以确定各种振转跃迁的能级和频率。我们的结果与实验结果吻合良好。例如，精确再现了508条谱线的红外跃迁，总均方根误差仅为0.105 cm(-1)。
