The Jahn–Teller effect in the presence of partial isotopic substitution: the 1E′′ state of NH2D and NHD2

Literature Information

Publication Date 2015-04-30
DOI 10.1039/C5CP01299F
Impact Factor 3.676
Authors

Ashim Kumar Saha, Gautam Sarma, Chung-Hsin Yang, Sebastiaan Y. T. van de Meerakker, David H. Parker, Colin M. Western


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Abstract

Rotationally resolved resonance enhanced multiphoton ionisation spectra of the 1E′′ state of NH2D are presented and analysed. The analysis indicates a small (34.9 cm−1) lifting of the vibronic degeneracy of the zero point level, approximately equal in sign but opposite in magnitude to the splitting observed in NHD2 in previous work. This observation is consistent with previous measurements on systems with partial isotopic substitution subject to a mild Jahn–Teller effect. A model is developed to calculate the splitting induced by asymmetric isotopic substitution of a degenerate electronic state, based on a harmonic force field with linear and quadratic Jahn–Teller terms added. The force field is developed in internal co-ordinates to allow the same parameters to be used to calculate the pattern of vibronic levels for all four isotopologues. The lifting of the degeneracy of the zero point level on asymmetric substitution comes from the quadratic Jahn–Teller effect; the linear term does not lift the degeneracy.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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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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