Local intermolecular structure, hydrogen bonding and related dynamics in the liquid cis/trans N-methylformamide mixture: A density functional theory based Born-Oppenheimer molecular dynamics study

The local intermolecular structure and related dynamics in the liquid cis/trans N-methylformamide mix-ture at ambient temperature and density conditions have been systematically studied by employing Born-Oppenheimer molecular dynamics simulation techniques. Particular attention has been paid to the local structure around the cis-and trans-conformers and the formation and dynamics of hydrogen bonds with their closest neighbors. The calculated atom-atom radial distribution functions are in very good agreement with available experimental data and reveal the existence of different types of hydrogen bonding intermolecular interactions. The average number of hydrogen bonds formed by the cis- conform-ers is higher in comparison with the one corresponding to the trans-conformers. Moreover, the lifetimes of the hydrogen bonds formed in the liquid are longer when the cis-conformers participate in the bond formation, either as donors or acceptors. These findings clearly indicate that the local structural network around the cis-conformers in the liquid is more cohesive. The latter finding is also reflected in the slower reorientational dynamics of the cis-conformers and the low-and high-frequency region of the spectral densities of the atomic velocity time correlation functions. Finally, the calculated average dipole moments of the trans-and cis-conformers are significantly higher than their corresponding gas-phase values, signifying the importance of polarization effects in this particular polar liquid solvent.(c) 2022 Elsevier B.V. All rights reserved.