Molecular ring rotation in poly(vinylferrocene)

Literature Information

Publication Date 2016-10-11
DOI 10.1039/C6CP05156A
Impact Factor 3.676
Authors

Bernhard Frick, Johannes Elbert, Markus Gallei, Bernd Stühn


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Abstract

We investigate the ring rotation dynamics in poly(vinylferrocene) (PVFc) using incoherent neutron spectroscopy. PVFc contains ferrocene units laterally attached to a polymer backbone, allowing for one cyclopentadienyl ring of the organometallic sandwich structure of ferrocene to undergo rotational jump diffusion. The barrier of rotation is found to be broadly distributed, but the dynamics can be well described using a rotation rate distribution model which is well known from the description of methyl group rotation in glassy polymers. As necessary information for the analysis of quasielastic scattering data, we measure the static structure factor of the polymer using polarized neutron diffraction. Neutron time-of-flight and backscattering data are then combined and consistently modeled over the large temperature range from 80 K to 350 K yielding an Arrhenius behavior of the jump rate distribution. The mean value of potential barrier distribution is found to be 〈EA〉 = 9.61(2) kJ mol−1 with a root mean square width of σE = 3.12(1) kJ mol−1, being the result of superposition of constant intramolecular and heterogeneous intermolecular rotational barriers.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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