Adjacent gauche stabilization in linear alkanes: implications for polymer models and conformational analysis.

Jeffery B Klauda; Richard W Pastor; Bernard R Brooks

doi:10.1021/jp0527608

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Adjacent gauche stabilization in linear alkanes: implications for polymer models and conformational analysis.

Jeffery B Klauda·Richard W Pastor·Bernard R Brooks

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Abstract

High-level ab initio quantum mechanical calculations are used to study various gauche conformational energies of n-pentane to n-decane. The destabilizing "pentane effect" (adjacent gauche states of opposite sign) for alkanes is confirmed, but the energies were found to depend slightly on chain length. In contrast, introducing an adjacent gauche of the same sign requires only 0.22-0.37 kcal/mol, approximately half of the single gauche state energy. This adjacent gauche stabilization should be taken into account when formulating or analyzing rotational isomeric models, carrying out conformational analysis, and developing force fields for alkanes, lipids, and related polymers.

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Alkanes Models, Chemical Models, Molecular Molecular Conformation Polymers Letter

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Jeffery B Klauda, Richard W Pastor, Bernard R Brooks. 2005-08-25. Adjacent gauche stabilization in linear alkanes: implications for polymer models and conformational analysis.. https://doi.org/10.1021/jp0527608

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