Molecular conformation of \(n\)-alkanes using terrain/funneling methods. (English) Zbl 1279.90134

Gattupalli, Rajeswar R.; Lucia, Angelo

J. Glob. Optim. 43, No. 2-3, 429-444 (2009).

Summary: Understanding molecular conformation is a first step in understanding the waxing (or formation of crystals) of petroleum fuels. In this work, we study the molecular conformation of typical fuel oils modeled as pure \(n\)-alkanes. A multi-scale global optimization methodology based on terrain methods and funneling algorithms is used to find minimum energy molecular conformations of united atom \(n\)-alkane models for diesel, home heating, and residual fuel oils. The terrain method is used to gather average gradient and average Hessian matrix information at the small length scale while funneling is used to generate conformational changes at the large length scale that drive iterates to a global minimum on the potential energy surface. In addition, the funneling method uses a mixture of average and point-wise derivative information to produce a monotonically decreasing sequence of objective function values and to avoid getting trapped at local minima on the potential energy surface. Computational results clearly show that the calculated united atom molecular conformations are comprised of zigzag structure with considerable wrapping at the ends of the molecule and that planar zigzag conformations usually correspond to saddle points. Furthermore, the numerical results clearly demonstrate that our terrain/funneling approach is robust and fast.

MSC:

90C26	Nonconvex programming, global optimization
92E99	Chemistry

Keywords:

multi-scale global optimization; terrain methods; funneling methods; \(n\)-alkane molecular conformation; fuel oils

Software:

Bonmin

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