Pseudo Jahn–Teller origin of cis–trans and other conformational changes. The role of double bonds
Literature Information
Pablo Garcia-Fernandez, Yang Liu, Isaac B. Bersuker, James E. Boggs
Based on the pseudo Jahn–Teller effect (PJTE) theory, an approach is developed to rationalize and predict the conformations and conformational changes in molecular systems with a common pattern, a double bond. It is shown that starting with the high-symmetry geometry of the environment (in many cases D2d), the double bond descends from an e2 electronic configuration (e is a twofold degenerate MO) which produces a variety of PJT distortions, the main of which is the rotational (b1) transformation D2d → D2h accompanied by the formation of the double bond. Further PJT interactions with higher energy E-states may trigger additional distortions which in D2h symmetry are classified as in-plane (ei) cis and trans, and out-of-plane (eo) chair and boat. The realization of these conformations depends on the positions of the excited E-states and the PJTE parameter values. The two emerging PJTE problems, (3A2 + 3E1 + 3E2) ⊗ (ei + eo) and (1A1 + 1B1 + 1B2 + 1E1 + 1E2) ⊗ (b1 + ei + eo), are formulated in the matrix form and provide a general picture of the ground and excited adiabatic potential energy surfaces. Following this scheme in combination with ab initio calculations, the possible conformations and conformational transitions are analyzed for several specific systems including (in increasing complexity) N2H2, C2H4, N2(NH2)2 and N2(C6H5)2 (azobenzene). The family of molecular systems with a double bond is vast, but the importance of the PJT approach developed here is also in its general validity as it can be applied to any other systems.
Recommended Journals
Related Literature
A quinone based single-molecule switch as building block for molecular electronics
Herbert Früchtl, Tanja van Mourik
DOI: 10.1039/D0CP06250B
A novel design of SiH/CeO2(111) van der Waals type-II heterojunction for water splitting
Jian Zeng, Bojun Peng, Zongle Ma, Ling-Ling Wang, Youwen Yang
DOI: 10.1039/D0CP05238H
Topological semimetal state with triply degenerate nodal points in a stable Cu2Te structure
Yiming Mi
DOI: 10.1039/D0CP05622G
Multiscale exploration of hydrocarbon adsorption and hopping through ZSM-5 channels – from Monte Carlo modelling to experiment
Maciej Strzempek, Karolina Tarach, Kinga Góra-Marek, Fernando Rey, Miguel Palomino, Susana Valencia, Witold Piskorz
DOI: 10.1039/D0CP05128D
Reactivity of dicationic N-heterocyclic chalcogen carbene analogues with methane and ethene: a theoretical investigation
Tsung-Lung Li, Zheng-Feng Zhang
DOI: 10.1039/D0CP06173E
A reliable and efficient resonance theory based on analysis of DFT wave functions
DOI: 10.1039/D0CP06207C
The quantitative impact of fluid vs. solid interfaces on the catalytic performance of pickering emulsions
Sebastian Stock, Annika Schlander, Maresa Kempin, Ramsia Geisler, Dmitrij Stehl, Kai Spanheimer, Nicole Hondow, Stuart Micklethwaite, Ariane Weber, Reinhard Schomäcker, Anja Drews, Markus Gallei, Regine von Klitzing
DOI: 10.1039/D0CP06030E
Membrane packing defects in synaptic vesicles recruit complexin and synuclein
Jie Liu, Bing Bu, Michael Crowe, Dechang Li, Jiajie Diao, Baohua Ji
DOI: 10.1039/D0CP03546G
What does graphitic carbon nitride really look like?
Sigismund T. A. G. Melissen, Tangui Le Bahers, Stephan N. Steinmann
DOI: 10.1039/D0CP06063A
You might also like
How is Ethyl 4-chlorothieno[2,3-b]pyridine-5-carboxylate (CAS: 59713-58-5) typically synthesized?
Ethyl 4-chlorothieno[2,3-b]pyridine-5-carboxylate (CAS: 59713-58-5) can be synth...
What regulatory guidelines apply to 5-Methyl-1H-indole-3-carbaldehyde (CAS: 52562-50-2)?
5-Methyl-1H-indole-3-carbaldehyde (CAS: 52562-50-2) is subject to various regula...
What are the physical and chemical properties of (1,3-Dimethyl-2,4-dioxo-1,2,3,4-tetrahydro-5-pyrimidinyl)boronic acid (CAS: 223418-73-3)?
(1,3-Dimethyl-2,4-dioxo-1,2,3,4-tetrahydro-5-pyrimidinyl)boronic acid is a white...
How should waste containing Sulfocostunolide A (CAS: 1016983-51-9) be handled?
Waste containing Sulfocostunolide A (CAS: 1016983-51-9) should be handled with c...
What precautions should be taken when handling Murraxocin (CAS: 88478-44-8)?
When handling Murraxocin (CAS: 88478-44-8), ensure proper personal protective eq...
What are the physical and chemical properties of Formvar (CAS: 63148-64-1)?
Formvar (CAS: 63148-64-1) is an alkyd resin characterized by a high molecular we...
Is (S)-4-benzyl-2-((benzyloxy)methyl)morpholine (CAS: 205242-66-6) safe?
(S)-4-benzyl-2-((benzyloxy)methyl)morpholine is generally safe when handled with...
What industries use Methyl 1-(5-bromo-2-pyrimidinyl)cyclopropanecarboxylate (CAS: 1447607-69-3)?
Methyl 1-(5-bromo-2-pyrimidinyl)cyclopropanecarboxylate (CAS: 1447607-69-3) is p...
Is 2-Methyl-1-phenyl-1-propanamine hydrochloride (CAS: 24290-47-9) safe?
2-Methyl-1-phenyl-1-propanamine hydrochloride (CAS: 24290-47-9) is generally con...
How is 3-(4-Bromophenyl)-2-methylpropanoic acid (CAS: 66735-01-1) typically synthesized?
3-(4-Bromophenyl)-2-methylpropanoic acid is synthesized through a multi-step pro...
Source Journal
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.














![4-[(1-Methyl-1H-pyrrol-2-yl)methylene]-1,3(2H,4H)-isoquinolinedione structure 4-[(1-Methyl-1H-pyrrol-2-yl)methylene]-1,3(2H,4H)-isoquinolinedione structure](https://static.chemtradehub.com/structs/110/1104546-89-5-a600.webp)