Binding energies and isomer distribution of neutral acetonitrile clusters

Abstract

AbstractStructures and relative stabilities of neutral acetonitrile clusters up to decamer have been investigated. We used the ABCluster code to thoroughly explore the potential energy surfaces (PESs) of the acetonitrile clusters and to generate initial geometries, which are further fully optimized at the MN15/6‐31++G(d,p) level of theory. Our exploration yielded several new local and global minima structures of the acetonitrile clusters. We located new global minimum structures of the acetonitrile pentamer to decamer. The results show that the PESs of the acetonitrile clusters are very flat, yielding several isoenergetic structures. Our investigations also revealed that the stability of the acetonitrile clusters is due both to CH⋯N and dipole–dipole interactions. Structures stabilized by the latter are found to be more stable than those stabilized by the former at low temperatures. Furthermore, we examined the effect of temperature on the stability of the structures of the acetonitrile clusters for temperatures in the range 20 to 400 K. We found that several structures contribute to the population of the clusters at high temperatures, and also that a significant contribution to the population comes from isomers that lie within 2.0 kcal/mol from the most stable one. In addition, we used the most stable structures to compute the binding energies of the acetonitrile clusters and to assess the performance of some DFT functionals (MN15, ωB97XD, PW6B95D3, and B2PLYP) in comparison with the MP2 method associated to the aug‐cc‐pVTZ basis set in calculating the binding energies. We found that the MN15 functional performs better than ωB97XD and PW6B95D3, and that MN15 is less sensitive to the basis set change. We also used an extrapolation scheme to calculate the binding energies of the acetonitrile clusters at the highly accurate W1BD, CBS‐QB3, and G4MP2 levels of theory. The resulting binding energies are recommended for future benchmarking of the acetonitrile clusters.