Vibrational Spectra and Structure of CH 3 Cl:(H 2 O) 2 and CH 3 Cl:(D 2 O) 2 Complexes. IR Matrix Isolation and ab Initio Calculations

The infrared spectra of CH 3 Cl + H 2 O isolated in solid neon at low temperature have been investigated. High concentration studies of water (0.01%−4%) and subsequent annealing lead to the formation of the ternary CH 3 Cl:(H 2 O) 2 complex. Detailed vibrational assignments were made on the observed spectra of water and deuterated water engaged in the complex. In parallel, structural, energetic, and vibrational properties of the complex have been studied at the second-order Møller−Plesset perturbation theory using several basis sets. Anaharmonic correction to the vibrational frequencies has been done with the standard second-order perturbation approach. It was shown that the ground state of the complex has a cyclic form for which the nonadditive three-body contribution was found to be around 10% of the interaction energy.