Ab initio potential-energy surface and rovibrational states of the HCN-HCl complex

A four-dimensional intermolecular potential-energy surface has been calculated for the HCN-HCl complex, with the use of the coupled cluster method with single and double excitations and noniterative inclusion of triples. Data for more than 13 000 geometries were represented by an angular expansion in terms of coupled spherical harmonics; the dependence of the expansion coefficients on the intermolecular distance R was described by the reproducing kernel Hilbert space method. The global minimum with De =1565 cm-1 and Re =7.47 a0 has a linear HCN-HCl hydrogen-bonded structure with HCl as the donor. A secondary hydrogen-bonded equilibrium structure with De =564 cm-1 and Re =8.21 a0 has a T -shaped geometry with HCN as the donor and the acceptor HCl molecule nearly perpendicular to the intermolecular axis. This potential surface was used in a variational approach to compute a series of bound states of the isotopomers HCN-H Cl35, DCN-H Cl35, and HCN-H Cl37 for total angular momentum J=0,1,2 and spectroscopic parities e, f. The results could be analyzed in terms of the approximate quantum numbers of a linear polyatomic molecule with two coupled bend modes, plus a quantum number for the intermolecular stretch vibration. They are in good agreement with the recent high resolution spectrum of Larsen [Phys. Chem. Chem. Phys. 7, 1953 (2005)] in the region of 330 cm-1 corresponding to the HCl libration. The (partly anomalous) effects of isotopic substitutions on the properties of the complex were explained with the aid of the calculations. © 2006 American Institute of Physics