On the nature of OH-stretching vibrations in hydrogen-bonded chains: Pump frequency dependent vibrational lifetime
Literature Information
Stephan Knop, Thomas La Cour Jansen, Jörg Lindner, Peter Vöhringer
Two-dimensional infrared spectroscopy was carried out on stereoselectively synthesized polyalcohols. Depending upon the stereochemical orientation of their hydroxyl groups, the polyols can either feature linear chains of hydrogen bonds that are stable for extended periods of time or they can display ultrafast dynamics of hydrogen-bond breakage and formation. In the former case, the OH-stretching vibrations and their transition dipoles are substantially coupled, hence prior to vibrational relaxation, the initial OH-stretching excitation is rapidly redistributed among the set of hydroxyl-groups constituting the hydrogen-bonded chain. This redistribution is responsible for an ultrafast loss of memory regarding the frequency of initial excitation and as a result, a pump-frequency independent vibrational lifetime is observed. In contrast, in the latter case, the coupling of the OH-groups and their transition dipoles is much weaker. Therefore, the OH-stretching excitation remains localized on the initially excited oscillator for the time scale of vibrational energy relaxation. As a result inhomogeneous relaxation dynamics with a pump-frequency-dependent lifetime are observed.
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Physical Chemistry Chemical Physics

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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