Ab initio molecular dynamics simulation of methanol and acetonitrile: The effect of van der Waals interactions

Citation:

Dias RF, da Costa CC, Manhabosco TM, de Oliveira AB, Matos MJS, Soares JS, Batista RJC. Ab initio molecular dynamics simulation of methanol and acetonitrile: The effect of van der Waals interactions. Chemical Physics Letters [Internet]. 2019;714 :172 - 177.

Abstract:

We employed PBE and BLYP semi-local functionals and the van der Waals density functional of Dion et al. (2004) (vdW-DF) to investigate structural properties of liquid acetonitrile and methanol. Among those functionals the vdW-DF is the only one that correctly predicts energy minima in inter-molecular interactions between acetonitrile molecules. We found that van der Waals interactions have a negligible effect on H-bonds in methanol chains. However, it significantly increases chain packing resulting in a more dense liquid in comparison to the other two functionals. The overall trend is that the vdW-DF tends to overestimate density and bulk modulus, meanwhile the semi-local functionals tend to underestimate density. Thus, van der Waals interactions play an important role in the properties of liquids in which much stronger dipole-dipole interactions are present.

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Last updated on 02/17/2019