Pseudo Jahn–Teller effect in the decasilanaphthalene molecule: Towards the origin of the buckling in silicene

Molina, B.; Soto, J. R.; Castro, Jorge

doi:10.1016/j.chemphys.2015.05.005

Cited by 7 publications

(7 citation statements)

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“…Irrespective of the magnitude of the energy differences (large or small) between the PJT active OMO-UMO/occupied crystal orbital (OCO)-unoccupied crystal orbital (UCO) pairs, no orbital combination can be eliminated solely based on high energy gap. As already discussed in equation 2, the PJT instability condition is affected by three key factors: the energy gap, the VCC and the primary force constant of the ground state [14,19]. Surely, the probability that the effect of the energy gap may be overruled by the strength of the other two factors cannot be ruled out.…”

Section: Resultsmentioning

confidence: 97%

“…Previous theoretical calculations by our group [11][12][13] and Molina et al [14] and Soto et al [15,16] have shown that silicene, germanene and stanene have inherent out-of-plane distortions in their structures. The cluster models predict an average puckering angle of 33.7 • for Si 6 H 6 at B3PW91/TZVP level of theory [13] and for Ge 6 H 6 , the buckling angle (torsional angle defined by any four adjacent Ge atoms) is 48. at PBE0 level [11].…”

Section: Introductionmentioning

confidence: 99%

“…Bersuker [17] has established that the deviations from planarity in electronically non-degenerate molecules occur solely due to the pseudo-Jahn-Teller effects (PJTEs). PJTE has been attributed to the distortions in several molecular systems [11][12][13][14][15][16]18] and therefore can be a unifying concept to explain structural diversity in many molecules and materials [17,[19][20][21].…”

Section: Introductionmentioning

confidence: 99%

“…In the last decade, Sato and co-workers [24][25][26][27][28] have successfully developed the theory of vibronic coupling density (VCD) to study the vibronic coupling and consequently PJTE of several molecular systems like C 3 H 3 [24], NH 3 [24], anthracene [24], naphthalene anion [28], bi-benzene [29], cyclopentadienyl radical [30] and decasilanaphthalene [14] among others. VCD has also been successful at predicting the chemical reactivity of giant molecules like fullerenes, including C 60 [2] and C 70 [27,31].…”

Section: Introductionmentioning

confidence: 99%

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Pseudo-Jahn–Teller effects in two-dimensional silicene, germanene and stanene: a crystal orbital vibronic coupling density analysis

Ghosh

Datta

2018

Bull Mater Sci

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The presence of the pseudo-Jahn-Teller (PJT) effect has been investigated in the heavier analogues of graphene, namely silicene, germanene and stanene, by applying the orbital vibronic coupling density theory. In order to do so, we have made a visa -vis analogy with their respective planar, honeycomb molecular cluster models, namely hexasilabenzene (Si 6 H 6), hexagermabenzene (Ge 6 H 6) and hexastannabenzene (Sn 6 H 6). One-to-one mapping of the occupied crystal orbitals and unoccupied crystal orbitals in two-dimensional (2D) Si, Ge and Sn systems to the occupied molecular orbitals and unoccupied molecular orbitals of the corresponding molecular units are used to identify PJT-active bands and compute the crystal orbital vibronic coupling density (c-OVCD) and crystal orbital vibronic coupling constants (c-OVCCs). c-OVCD and c-OVCC show the local picture of the PJT coupling in these 2D systems. This article exemplifies the fruitfulness of deciphering the structural aspects in materials based on orbitals of their corresponding simple molecular units-a reductionist quantum chemical approach to materials.

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Section: Resultsmentioning

confidence: 97%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

Section: Introductionmentioning

confidence: 99%

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Pseudo-Jahn–Teller effects in two-dimensional silicene, germanene and stanene: a crystal orbital vibronic coupling density analysis

Ghosh

Datta

2018

Bull Mater Sci

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“…In applications to molecules and solids, the spontaneous symmetry breaking is induced via the proper Jahn–Teller effect (JTE), Renner–Teller effect (RTE), and pseudo JTE (PJTE) . In particular, as the most important extension of the traditional JTE theory, the PJTE has played significant role in elucidating the instability and distortions of polyatomic systems in nondegenerate states and degenerate states . Therefore, not only the symmetry breaking phenomenon from planar to bird‐like structure in neutral halogenabenzene but also the process of restoring to be planar in halogenabenzene cations, relate to the well‐known Jahn–Teller vibronic coupling effect.…”

Section: Introductionmentioning

confidence: 99%

Pseudo Jahn–Teller origin tracking for symmetry breaking in halogenabenzene: How can a bird fly?

Wang

Liu

Zheng

2018

Int J of Quantum Chemistry

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The cyclic iodabenzene molecule (CH) 5 I was first introduced and characterized as planar configuration and zwitterionic valence structure by Glukhovtsev in 1991. Recently, it caused researchers' great interest due to the theoretical discovery of a stable bird-like structure by Hoffmann et al. in 2017 which has similar electronic structure and charge distribution as wellknown Meisenheimer complex C 6 H − 7 . Inspired by this, we continue to tell the halogenabenzene story by revealing the origin of the bird-like structure and understanding how the electronic behavior affects the geometrical symmetry for a molecule. By combining the Pseudo Jahn-Teller effect (PJTE) theory with the ab initio calculations for halogenabenzenes (CH) 5 X (X = F, Cl, Br, I) and C 6 H − 7 , it is illustrated that the vibronic coupling of 1 A 1 ground state and 1 B 1 excited states with C 2v planar structure along the out-of-plane b 1 distortion triggers the symmetry breaking of planar configuration to form a preferred bird-like structure. This interpretation can be also applied to explain their different stabilization energies by analyzing numerically the energy gaps of coupled electronic states and PJTE vibronic coupling parameters. Taking use of the PJTE formulation above, we also tracked the origin of restoring to be planar for (CH) 5 X 2+ cation, as well as their isoelectronic species (CH) 5 O + and (CH) 5 N, and suggests an effective strategy to stabilize the planar configuration for halogenabenzenes. K E Y W O R D S excited state, halogenabenzene, pseudo Jahn-Teller effect, symmetry breaking, vibronic coupling 1 | INTRODUCTIONWhen referring to halogen-substituted benzene compounds, most of attention has been paid to the cases that hydrogen atoms in different positions of benzene are substituted for halogen atoms, such as C 6 H 5 X [1][2][3][4] and C 6 H 4 X 2 or C 6 X 6 [2-7] (X = F, Cl, Br, I). In contrast, the systems in which the carbon atom is replaced by halogen atom have been rarely reported. The cyclic (CH) 5 I molecule, called iodabenzene, was firstly introduced by Glukhovtsev in 1991 and found to show a planar configuration with 8π electron system based on the semiempirical AM1 and MNDO calculations. [8] More recently, Hoffmann and his coworkers performed more accurate DFT and MP2 calculations on iodabenzene and obtained a stable bird-like minimum structure, which is expected optimistically to be detected and isolated in experiment. [9] It was also described that iodabenzene and its analogues (CH) 5 X (X = F, Cl, Br) have the similar geometric configuration and zwitterionic valence electronic structure to the famous Meisenheimer complexes. [10,11] Besides the neutral halogenabenzene molecules, the cation (CH) 5 X 2+ (X = F, Cl, Br, I), as well as their iso-valence electronic pyrylium cation (CH) 5 O + and pyridine (CH) 5 N, also attracted great interest in literatures. [12][13][14][15] As very common chemical reagents, (CH) 5 O + and (CH) 5 N are applied extensively in the field of organic chemistry. The (CH) 5 O + is used ...

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Rise of silicene: A competitive 2D material

Zhao

Liu

et al. 2016

Progress in Materials Science

795

477

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Pseudo Jahn–Teller effect in the decasilanaphthalene molecule: Towards the origin of the buckling in silicene

Cited by 7 publications

References 30 publications

Pseudo-Jahn–Teller effects in two-dimensional silicene, germanene and stanene: a crystal orbital vibronic coupling density analysis

Pseudo-Jahn–Teller effects in two-dimensional silicene, germanene and stanene: a crystal orbital vibronic coupling density analysis

Pseudo Jahn–Teller origin tracking for symmetry breaking in halogenabenzene: How can a bird fly?

Rise of silicene: A competitive 2D material

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