Domain Based Pair Natural Orbital Coupled Cluster Studies on Linear and Folded Alkane Chains.

Abstract

In this study the question of what is the last unbranched alkane that prefers a linear conformation over a folded one is revisited from a theoretical point of view. Geometries have been optimized carefully using the most accurate theoretical approach available to date for such systems, namely, doubly hybrid density functional theory in conjunction with larger quadruple-ζ quality basis sets. The resulting geometries deviate significantly from previously reported ones and have a significant impact on the predicted energetics. Electronic energies were calculated using the efficient and accurate domain local pair natural orbital coupled cluster method with single-, double-, and triple substitutions (DLPNO-CCSD(T)) electronic structure method. Owing to the method's efficiency, we were able to employ up to quadruple-ζ quality basis sets for all hydrocarbons up to C19H40. In conjunction with carefully designed basis set extrapolation techniques, it is estimated that the electronic energies reported in this study deviate less than 1 kJ/mol from the canonical CCSD(T) basis set limit. Thermodynamic corrections were calculated with the PW6B95-D3 functional and the def2-QZVP basis set. Our prediction is that the last linear conformer is either C16H34 or C17H36 with the latter being more probable. C18H38 can be safely ruled out as the most stable isomer at 100 K. These findings are in agreement with the elegant experimental studies of Suhm and co-workers. Deviations between the current and previous theoretical results are analyzed in detail.