| Abstract
| - A new synthetic approach for the formation of ultrathin polymer films with customizable propertieswas developed. In this approach, the kinematic nature of proton collisions with simple organic moleculescondensed on a substrate is exploited to break C−H bonds preferentially. The subsequent recombinationof carbon radicals gives a cross-linked polymer thin film, and the selectivity of C−H cleavage preservesthe chemical functionalities of the precursor molecules. The nature and validity of the method are exemplifiedwith theoretical results from ab initio molecular dynamics calculations and experimental evidence from avariety of characterization techniques. Its applicability is demonstrated by the synthesis of ultrathin polymerfilms with precursor molecules such as dotriacontane, docosanoic acid, poly(acrylic acid) oligomer, andpolyisoprene. The approach is fundamentally different from conventional chemical synthesis as it involvesan unusual mix of physical and chemical processes including charge exchange, projectile penetration,kinematics, collision-induced dissociation, inelastic energy transfer, chain transfer, and chain cross-linking.
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