Photoelectron spectroscopic study of 2-naphthylnitrene and its thermal rearrangement to cyanoindenes
Literature Information
Mayank Saraswat, Adrian Portela-Gonzalez, Enrique Mendez-Vega, Ginny Karir, Wolfram Sander, Patrick Hemberger
2-Cyanoindene has recently been identified in the interstellar medium, however current models cannot fully account for its formation pathways. Herein, we identify and characterize 2-naphthylnitrene, which is prone to rearrange to 2- and 3-cyanoindene, in the gas phase using photoion mass-selective threshold photoelectron spectroscopy (ms-TPES). The adiabatic ionization energies (AIE) of triplet nitrene (3A′′) to the radical cation in its lowest-energy doublet +(2A′) and quartet ã+(4A′) electronic states were determined to be 7.72 ± 0.02 and 8.64 ± 0.02 eV, respectively, leading to a doublet–quartet energy splitting (ΔED–Q) of 0.92 eV (88.8 kJ mol−1). A ring-contraction mechanism yields 3-cyanoindene, which is selectively formed under mild pyrolysis conditions (800 K), while the lowest-energy isomer, 2-cyanoindene, is also observed under harsh pyrolysis conditions at 1100 K. The isomer-selective assignment was rationalized by Franck–Condon spectral modeling and by measuring the AIEs at 8.64 ± 0.02 and 8.70 ± 0.02 eV for 2- and 3-cyanoindene, respectively, in good agreement with quantum chemical calculations.
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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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