Liquid structures of chloroethenes from molecular simulations and electronic structure calculations

Abstract

The structures of six liquid chloroethenes viz., chloroethene, 1,1-Dichloroethene, cis- and trans-1,2-Dichloroethene, trichloro- and tetrachloroethene, are explored using the all-atom molecular dynamics simulations, molecular simulations with the 3D-reference interaction site model and the Kovalenko-Hirata closure relation (3D-RISM-KH), and dispersion corrected density functional theory. The liquid structures have different local orientations stabilized by possible π-stacking, π⋅⋅⋅Cl, and H⋅⋅⋅Cl intermolecular interactions. The RISM computations and MD simulations are in good agreement with each other, and provided important structural details. The electronic structure calculations support the presence of dimeric structures in the liquid form as well as the findings from the molecular simulations.