Simulation Investigation of Bulk and Surface Properties of Liquid Benzonitrile: Ring Stacking-Assessment and Deconvolution.

The content and the molecular dynamics (MD) simulation analysis here are inspired by our recent ab initio calculation on benzonitrile (BZN), whereas the present results are to expand and develop macroscopic documentation involving data verification. MD simulations of the bulk liquid BZN in the range of 293-323 K unravel the hydrogen bond (-C≡N···H) formation with strength in the order of ortho -H ≫ meta -H ∼> para -H. The possibility for ortho -Hs to get involved in the formation of two bonds simultaneously confirms each having σ- and π-bonding features. Accordingly, we used vast efforts for structural analysis particularly based on the deconvolution of the corresponding complex correlation functions. Specific angle-dependent correlation functions led to the recognition of the molecular stacking with a strict anti-parallel orientation. The in-plane dimer and trimer also take part in the structural recognition. A singularity, found in the trend of the simulated temperature-dependent viscosity and diffusion coefficient of liquid BZN, is centered at about 313 K and quite fascinatingly emulates the reported experiment viscosity. An interplay between a small change in the trend of density and a large change in the corresponding viscosity is a key factor in supporting the singularity. Deconvolution of the simulation results allows attributing the singularity to structural alteration involving H-bonding of different types and extent. Approaching the range of 308-313 K, an alteration between hydrogen bond formation involving mostly ortho -Hs and mixed ortho -Hs + meta -H is possible and supports the singularity.