Vibrations and hydrogen bonding in porphycene

Literature Information

Publication Date 2012-02-21
DOI 10.1039/C2CP24098J
Impact Factor 3.676
Authors

Sylwester Gawinkowski, Łukasz Walewski, Alexander Vdovin, Alkwin Slenczka, Stephane Rols, Mark R. Johnson, Jacek Waluk


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Abstract

Combined use of IR, Raman, neutron scattering and fluorescence measurements for porphycene isolated in helium nanodroplets, supersonic jet and cryogenic matrices, as well as for solid and liquid solutions, resulted in the assignments of almost all of 108 fundamental vibrations. The puzzling feature of porphycene is the apparent lack of the N–H stretching band in the IR spectrum, predicted to be the strongest of all bands by standard harmonic calculations. Theoretical modeling of the IR spectra, based on ab initio molecular dynamics simulations, reveals that the N–H stretching mode should appear as an extremely broad band in the 2250–3000 cm−1 region. Coupling of the N–H stretching vibration to other modes is discussed in the context of multidimensional character of intramolecular double hydrogen transfer in porphycene. The analysis can be generalized to other strongly hydrogen-bonded systems.

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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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