On the vibronic level structure in the NO3 radical Part III. Observation of intensity borrowing via ground state mixing

Literature Information

Publication Date 2009-05-18
DOI 10.1039/B902252J
Impact Factor 3.676
Authors

John F. Stanton, Mitchio Okumura


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Abstract

The Ã2E″← 2A′2 absorption spectrum exhibits vibronically allowed transitions from the ground state of NO3 to upper state levels having a″1 and e′ vibronic symmetries. This paper explores the coupling mechanisms that lend intensities to these features. While transitions to e′ vibronic levels borrow intensity from the very strong 2E′← 2A′2 electronic transition, those to a″1 levels involve only negligible upper-state borrowing effects. Rather, it is the vibronic mixing of the ground vibronic level of NO3 with vibrational levels in the 2E′ electronic state that permit the a″1 levels to be seen in the spectrum. These ideas are supported by vibronic coupling calculations. The fact that the intensities of features corresponding to the two different vibronic symmetries are comparable is thus accidental.

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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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