The electronic spectrum of linear pentadiynylidene in comparison with isomeric ethynylcyclopropenylidene
文献信息
Andreas Mavrandonakis, Max Mühlhäuser, George E. Froudakis, Sigrid D. Peyerimhoff
Approximate transition energies and oscillator strengths are computed with large-scale multi-reference configuration interaction calculations to differentiate between linear pentadiynylidene HC5H and its Cs symmetric isomer ethynylcyclopropenylidene HC3C2H by certain fingerprints in their electronic spectra. The first dipole-allowed transition of the HC5H spectrum is obtained at 2.76 eV (3Σ−u ← X 3Σ−g) in reasonable agreement with experimental measurements of 434 nm (2.86 eV) in neon matrix. The oscillator strength of 3Σ−u ← X 3Σ−g of linear HC5H is computed with f = 0.007, a value similar to what we obtain for linear HC7H (f = 0.005). In addition a second very strong 3Σ−u ← X3Σ−g transition is predicted by the calculations around 7.3 eV. The yet-to-be-observed electronic spectrum of HC3C2H is characterized by four strong transitions calculated at 4.79 eV (2 1A″), 6.17 eV (2 1A′), 7.27 eV (3 1A′) and 7.74 eV (4 1A′). The first transition of HC3C2H 1 1A″ ← X 1A′ is calculated to be very weak and at much higher energy (3.64 eV) than the first 3Σ−u ← X 3Σ−g transition of the linear isomer.
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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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