Journal of Chemical Physics, Vol.109, No.23, 10284-10292, 1998
Ab initio potential energy surface and rovibrational spectra of He-CO2
The potential energy surface for the He-CO2 van der Waals complex is calculated using the fourth-order Moller-Plesset (MP4) perturbation theory with a large basis set containing bond functions. The interaction energies are obtained by the supermolecular approach with the full counterpoise correction for the basis set superposition error. The MP4 interaction energies are then fitted to an exponential-spline-Morse-Morse-spline-van der Waals potential form. The ab initio potential energy surface contains two local minima corresponding to the T-shaped and linear structures. The T-shaped minimum is the global minimum with the well depth of 44.41 cm(-1) at R(He-C) = 3.10 Angstrom. The linear minimum has a well depth of 27.69 cm(-1) at R(He-C) = 4.26 Angstrom. A potential barrier that separates the two minima is located at R(He-C) = 4.10 Angstrom and theta = 39 degrees with a height of 19.81 cm(-1). The rovibrational energy levels of He-CO2 with CO2 at its ground state and upsilon(3) excited state are calculated using the vibrational self-consistent field configuration-interaction approach. Our calculated results show that the potential supports five vibrational bound slates. The zero-point energy is 28.60 cm(-1). The first excited bend frequency is 8.67 cm(-1), which is very close to the experimental estimated value of about 9 +/- 2 cm(-1). The calculated transition frequencies and spectroscopic constants are in good agreement with the experimental values.
Keywords:HIGH-RESOLUTION SPECTROSCOPY;RARE GAS-CO2 COMPLEXES;DER-WAALSCOMPLEXES;VANDERWAALS COMPLEXES;VIBRATIONAL PREDISSOCIATION;MICROWAVE SPECTROSCOPY;BOUND-STATES;ELECTRON-GAS;BASIS-SETS;AR