Pseudo Jahn–Teller effect in stacked benzene molecules

Boltrushko, V.; Krasnenko, Veera; Hizhnyakov, V.

doi:10.1016/j.chemphys.2015.03.006

Cited by 7 publications

(4 citation statements)

References 28 publications

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“…In our case of nondegenerate electronic states the PJTE provides a reasonable picture of the structure and properties of the compounds under consideration. The method has been successfully applied to more simple carbon and silicon four-membered ring systems, such as C 4 H 4 20 , C 4 F 4 7 , Si 4 21 , Si 4 H 4 2+ 22 , as well as to a variety of other molecular systems (see 18 23 24 25 26 27 28 29 30 and references therein).…”

mentioning

confidence: 99%

Geometry, Electronic Structure, and Pseudo Jahn-Teller Effect in Tetrasilacyclobutadiene Analogues

Liu

Wang

Берсукер

2016

Sci Rep

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We revealed the origin of the structural features of a series of tetrasilacyclobutadiene analogues based on a detailed study of their electronic structure and the pseudo Jahn-Teller effect (PJTE). Starting with the D4h symmetry of the Si4R4 system with a square four-membered silicon ring as a reference geometry, and employing ab initio calculations of energy profiles along lower-symmetry nuclear displacements in the ground and several excited states, we show that the ground-state boat-like and chair-like equilibrium configurations are produced by the PJT interaction with appropriate excited sates. For Si4F4 a full two-mode b1g−b2g adiabatic potential energy surface is calculated showing explicitly the way of transformation from the unstable D4h geometry to the two equilibrium C2h configurations via the D2h saddle point. The PJTE origin of these structural features is confirmed also by estimates of the vibronic coupling parameters. For Si4R4 with large substituents the origin of their structure is revealed by analyzing the PJT interaction between the frontier molecular orbitals. The preferred chair-like structures of Si4R4 analogues with amido substituents, and heavier germanium-containing systems Ge4R4 (potential precursors for semiconducting materials) are predicted.

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confidence: 99%

Geometry, Electronic Structure, and Pseudo Jahn-Teller Effect in Tetrasilacyclobutadiene Analogues

Liu

Wang

Берсукер

2016

Sci Rep

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“…Bz(Ar) 2 (parallel) showed the compressed form, whereas Bz(Ar) 2 (perpendicular) showed the elongated one. These results indicate that a slight positional change of the argon atoms strongly affected the structural forms of Bz + , after the ionization of Bz(Ar) 2 .…”

Section: Hyperfine Couplingmentioning

confidence: 80%

“…The Jahn–Teller (J–T) effect is frequently found in several chemical and physical systems. − The coupling between degenerate electronic states and asymmetric vibrations results in the energy minimum of the molecule being located in geometric structures with lower symmetry.…”

Section: Introductionmentioning

confidence: 99%

Jahn–Teller Effect of the Benzene Radical Cation: A Direct ab Initio Molecular Dynamics Study

Tachikawa

2018

J. Phys. Chem. A

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The benzene radical cation (Bz) is a typical model molecule of the Jahn-Teller (J-T) active species. Bz has two structural forms due to the J-T effect. These are the compressed and elongated forms, expressed as Bz(comp) and Bz(elong), respectively. In Bz(comp), the hexagonal structure of the benzene ring is compressed up and down, and in Bz(elong), it is pulled up and down. From electron spin resonance experiments, it was found that Bz takes a compressed form in low-temperature Freon matrices (CFCl and CFClCFCl), whereas the elongated form was found in argon matrices. However, the selectivity of these structural forms is still unclear. In this study, the ionization dynamics of isolated benzene (Bz) and benzene-M complexes (where M denotes counter-molecules, M = NH, HO, CFCl, CH, CHOH, Ar, SH, ammonia dimer, or water dimer) have been investigated by means of the direct ab initio molecular dynamics (AIMD) method in order to shed light on the Bz formation mechanism. The static ab initio calculations showed that Bz(comp) is slightly more energetically stable than Bz(elong), although the energy difference was only 0.1 kcal/mol at the CCSD/6-311++G(d,p) level. The direct AIMD calculations indicated that Bz(comp) was formed from the Bz-M complexes when M was NH, CFCl, or an ammonia dimer, whereas the ionization of Bz-M when M was HO, CH, CHOH, SH or a water dimer formed Bz(elong). In the case of complexes with an argon dimer, Bz(Ar), both forms were obtained from a slight orientation change of Ar on Bz. A selective rule is discussed on the basis of the calculated results.

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“…extra chemical stability of aromatic rings, but they also introduce the possibility of interactions between the molecular orbitals and other chemical entities such as cations or adjacent pi-type systems. Among other things, pi-bonding has been invoked to account for a tendency of certain aromatic compounds to form stacked arrangements (Small et al 2004;Boltrushko et al 2015). However, as discussed by Martinez and Iverson (2012) some related effects such as electrostatic attractions and polarization can be more important than the predicted effects due to the pi orbitals.…”

Section: Pi () Bondingmentioning

confidence: 99%

Self-assembly fundamentals in the reconstruction of lignocellulosic materials: A review

Hubbe

Trovagunta²,

Zambrano³

et al. 2023

BioRes

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This review article considers processes by which the main components of wood have been reported to arrange themselves into various kinds of organized structures, at least to a partial extent. The biosynthesis of wood provides the clearest examples of such self-organization. For example, even before a cellulose macromolecule has been completely synthesized in a plant organism, the leading parts of the polymer chains already will have assembled themselves into organized crystals, i.e., nano-fibrils. This review then considers a challenge that faces industrial engineers: how to emulate the great success of natural systems when attempting to achieve favorable materials properties, process efficiency, and environmental friendliness when developing new engineered wood structures, barrier films, and other desired products composed of lignocellulosic materials. Based on the reviewed literature, it appears that the main chemical components of wood, even after they have been isolated from each other, still have a remnant of their initial tendencies to come back together in a somewhat non-random fashion, following mechanisms that can be favorable for the production of engineered materials having potentially useful functions.

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Pseudo Jahn–Teller effect in stacked benzene molecules

Cited by 7 publications

References 28 publications

Geometry, Electronic Structure, and Pseudo Jahn-Teller Effect in Tetrasilacyclobutadiene Analogues

Geometry, Electronic Structure, and Pseudo Jahn-Teller Effect in Tetrasilacyclobutadiene Analogues

Jahn–Teller Effect of the Benzene Radical Cation: A Direct ab Initio Molecular Dynamics Study

Self-assembly fundamentals in the reconstruction of lignocellulosic materials: A review

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