The rotationally resolved electronic spectrum of p-cyanophenol
Literature Information
Jochen Küpper, Michael Schmitt, Karl Kleinermanns
The electronic origin transition of p-cyanophenol (4-hydroxy-benzonitrile) at 35547.46 cm−1 was examined using rotationally resolved LIF spectroscopy. The experimentally determined inertial parameters are reported and compared to the results of ab initio calculations. The S1-lifetime of p-cyanophenol is determined to be 10.6 ± 3 ns, considerably longer than the excited state lifetime of phenol (2.4 ns). This reduction of the rate of internal conversion compared to phenol is explained by different electronic coupling matrix elements for the internal conversion in phenol and p-cyanophenol. The barrier to internal rotation of the hydroxy group in the ground states is determined from the observed splitting of the rovibronic lines to 1420 ± 20 cm−1. This barrier is compared to values for the ground and first excited electronic state calculated by ab initio theory.
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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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