At What Chain Length Do Unbranched Alkanes Prefer Folded Conformations?

• Published in: The journal of physical chemistry. A, Molecules, spectroscopy, kinetics, environment, & general theory Vol. 118; no. 9; pp. 1706 - 1712
• Main Authors: Byrd, Jason N, Bartlett, Rodney J, Montgomery, John A
• Format: Journal Article
• Language: English
• Published: United States American Chemical Society 06-03-2014
• Subjects: Alkanes; Alkanes - chemistry; Approximation; Benchmarking; Chains; Energy use; Mathematical analysis; Molecular Conformation; Orbitals; Quantum Theory
• ISSN: 1089-5639; 1520-5215
• DOI: 10.1021/jp4121854

Short unbranched alkanes are known to prefer linear conformations, whereas long unbranched alkanes are folded. It is not known with certainty at what chain length the linear conformation is no longer the global minimum. To clarify this point, we use ab initio and density functional methods to compute the relative energies of the linear and hairpin alkane conformers for increasing chain lengths. Extensive electronic structure calculations are performed to obtain optimized geometries, harmonic frequencies, and accurate single point energies for the selected alkane conformers from octane through octadecane. Benchmark CCSD(T)/cc-pVTZ single point calculations are performed for chains through tetradecane, whereas approximate methods are required for the longer chains up to octadecane. Using frozen natural orbitals to unambiguously truncate the virtual orbital space, we are able to compute composite CCSD FNO(T) single point energies for all the chain lengths. This approximate composite method has significant computational savings compared to full CCSD(T) while retaining ∼0.15 kcal/mol accuracy compared to the benchmark results. More approximate dual-basis resolution-of-the-identity double-hybrid DFT calculations are also performed and shown to have reasonable 0.2–0.4 kcal/mol errors compared with our benchmark values. After including contributions from temperature dependent internal energy shifts, we find the preference for folded conformations to lie between hexadecane and octadecane, in excellent agreement with recent experiments [ Lüttschwager N. O. ; Wassermann T. N. ; Mata R. A. ; Suhm M. A. Angew. Chem. Int. Ed. 2013, 52, 463 ].