화학공학소재연구정보센터
Journal of Chemical Physics, Vol.121, No.6, 2630-2635, 2004
Ab initio potential energy surface and rovibrational spectrum of Ar-HCCCN
We report an ab initio intermolecular potential energy surface of the Ar-HCCCN complex using a supermolecular method. The calculations were performed using the fourth-order Moller-Plesset theory with the full counterpoise correction for the basis set superposition error and a large basis set including bond functions. The complex was found to have a planar T-shaped structure minimum and a linear minimum with the Ar atom facing the H atom. The T-shaped minimum is the global minimum with the well depth of 236.81 cm(-1). A potential barrier separating the two minima is located at R=5.57 Angstrom and theta=20.39degrees with the height of 151.59 cm(-1). The two-dimensional discrete variable representation was employed to calculate the rovibrational energy levels for Ar-HCCCN. The rovibrational spectra including intensities for the ground state and the first excited intermolecular vibrational state are also presented. The results show that the spectra are mostly b-type (DeltaK(a)=+/-1) transitions with weak a-type (DeltaK(a)=0) transitions in structure, which are in good agreement with the recent experimental results [A. Huckauf, W. Jager, P. Botschwina, and R. Oswald, J. Chem. Phys. 119, 7749 (2003)]. (C) 2004 American Institute of Physics.