Strong Pseudo Jahn–Teller Effect on the Single Hexagonal Unit of Germanene

MRS Advances ◽  
2016 ◽  
Vol 1 (22) ◽  
pp. 1591-1596 ◽  
Author(s):  
J. R. Soto ◽  
B. Molina ◽  
J. J. Castro
Keyword(s):  
Dft Calculations ◽  
Excited States ◽  
Density Functional ◽  
Coupling Model ◽  
Vibronic Coupling ◽  
Coupling Constants ◽  
Hybrid Functional ◽  
Jahn Teller ◽  
Jahn Teller Effect ◽  
Different Origins

ABSTRACTGermanene, the 2D graphene-like Ge nanosheet, has been recently the subject of many theoretical studies and experimental attempts to synthesize it on Ag(111), Au(111) and Pt(111) surfaces. The experimental and theoretical evidences of germanene show a 2D continuous honeycomb layer with a buckled conformation. Density functional theory (DFT) calculations have predicted a larger buckling for germanene than silicene whose origin is also associated with a pseudo Jahn–Teller (PJT) effect. In this work we show that despite the fact that both, silicene and germanene possess a buckled conformation with a PJT origin, their vibronic coupling have different origins. The analysis is based on the PJT puckering instability of the hexagermabenzene molecule, the single hexagonal unit of germanene. This is done through the linear vibronic coupling model between the ground and the lowest excited states, which leads to a puckering distortion of the more symmetric cluster. We study both, the multilevel superposition vibronic model and possible mixing of excited states of different irreducible representations, which have been used to show the origin of similar structural transitions in hexagonal silicon and gold ring systems respectively. We show that contrary to other cases with one six-member rings, for the hexagermabenzene molecule a mixture of both the multilevel PJT and a ground state coupling with two quasi-degenerate excited states is necessary for a satisfactory explanation of puckering. Our model allows a determination of the coupling constants and predicts simultaneously the Adiabatic Potential Energy Surface (APES) behavior for the ground and excited states around the maximum symmetry point. The analysis is based on a scalar relativistic DFT and time-dependent DFT (TD-DFT) calculations in the Zero Order Regular Approximation (ZORA) using the B3LYP hybrid functional.

Buckling on stanene: the role played by spin-orbit coupling and pseudo Jahn-Teller effect

MRS Advances ◽  
2017 ◽  
Vol 2 (29) ◽  
pp. 1563-1569 ◽  
Author(s):  
J. R. Soto ◽  
B. Molina ◽  
J. J. Castro
Keyword(s):  
Dft Calculations ◽  
Group Iv ◽  
Vibronic Coupling ◽  
Coupling Constants ◽  
Orbit Coupling ◽  
Teller Effect ◽  
Spin Orbit Coupling ◽  
Spin Orbit ◽  
Jahn Teller ◽  
Jahn Teller Effect

ABSTRACTTwo-dimensional group IV layers beyond graphene, as silicene, germanene and the Sn-based stanene, have been recently synthesized by molecular beam epitaxy. Density Functional Theyory (DFT) calculations predict low-buckled structures for these 2D nanosheets, with a hexagonal honeycomb conformation, typical of the graphene-like surfaces. The buckling parameter δ increases from Si to Sn-based layers, with a maximum predicted of 0.92 Å for stanene. High-buckled structures for these materials resulted to be unstable. We have previously shown that for silicene and germanene, the origin of the buckled structure resides on the pseudo Jahn-Teller puckering distortion, resulting from non-adiabatic effects. It has been shown that hexagermabenzene, the single hexagonal unit of germanene, is subject to a strong vibronic coupling whose origin is the pseudo Jahn-Teller effect. This coupling resulted to be around ten times larger than the one obtained for hexasilabenzene. For stanene, an additional effect needs to be considered to understand the origin of buckling: the spin-orbit coupling (SOC). This SOC contributes to open an electronic band gap, enabling the use of these layers as nanoelectronic components. In this work, we present an analysis based on DFT in the Zeroth-Order Regular Approximation (ZORA) for both scalar relativistic and spin-orbit versions that quantify the influence of the spin-orbit coupling in the puckering of Sn6H6. Also, under the linear vibronic coupling model between the ground and the lowest excited states, we present the pseudo Jahn-Teller contribution. The scalar ZORA approximation is used to perform time-dependent DFT calculations to incorporate the low-energy excitations contributions. Our model leads to the determination of the coupling constants and predicts simultaneously the Adiabatic Potential Energy Surface behavior for the ground and excited states around the maximum symmetry point. These values allow us to compare the Jahn-Teller relevance in buckling with the other group IV layers.

Pseudo Jahn–Teller origin of twisting in 3,6-pyridazinedione derivatives; N2C4H2Y2Z2 (Y = O, S, Se, Z = H, F, Cl, Br) compounds

2015 ◽  
Vol 14 (06) ◽  
pp. 1550045 ◽  
Author(s):  
Ali Reza Ilkhani
Keyword(s):  
Vibronic Coupling ◽  
Coupling Constants ◽  
Planar Configuration ◽  
Calculation Results ◽  
Jahn Teller ◽  
In Series ◽  
Jahn Teller Effect ◽  
Adiabatic Potential Energy Surface ◽  
The Difference ◽  
Breaking Symmetry

3,6-pyridazinedione and two of its derivatives where oxygen atoms of the molecule are substituted by two sulfur or selenium ( N 2 C 4 Y 2 H 4) were studied with the goal of answering the following question: "Which N 2 C 4 Y 2 H 4 compounds are unstable in their planar configuration?" Additionally, the origin of the twisting instability of 3,6-pyridazinedione planar configuration and three of its 1,2-dihalo derivatives ( N 2 C 4 H 2 O 2 Z 2) were rationalized by employing the pseudo Jahn–Teller effect (PJTE) to explain the difference between N 2 C 4 H 2 O 2 Z 2 structures in series. Therefore, the structures of six 3,6-pyridazinediones ( N 2 C 4 H 2 Y 2 Z 2) were optimized in both equilibrium and planar configurations, and their vibrational frequencies were calculated. Then the adiabatic potential energy surface (APES) profiles along the a2 distortion coordinates were calculated. Based on the calculation results, N 2 C 4 S 2 H 4 and N 2 C 4 Se 2 H 4 compounds were stable in the planar structure; but, due to the vibronic coupling interaction between the 1A1 ground state and the first excited state 1A2, the twisting instability occurred in planar N 2 C 4 H 2 O 2 Z 2 series. The (1 A 1 + 1 A 2) ⊗ a2 problem was found to be the reason of the breaking symmetry phenomena in all the four N 2 C 4 H 2 O 2 Z 2 in series from unstable planar configuration (highest-symmetry C 2v ) to the stable twisted geometry with C 2 symmetry. Finally, the vibronic coupling constants of the PJTE of the compounds in series were estimated by fitting the secular equation roots along the normal coordinates of distortion.

An alternative model of the vibronic coupling in octahedral complexes

1988 ◽  
Vol 53 (6) ◽  
pp. 1134-1140
Author(s):  
Martin Breza ◽  
Peter Pelikán
Keyword(s):  
Linear Regression ◽  
Alternative Model ◽  
Potential Surface ◽  
Analytical Formula ◽  
Coupling Model ◽  
Regression Method ◽  
Vibronic Coupling ◽  
Linear Regression Method ◽  
Active Systems ◽  
Jahn Teller

It is suggested that for some transition metal hexahalo complexes, the Eg-(a1g + eg) vibronic coupling model is better suited than the classical T2g-(a1g + eg) model. For the former, alternative model, the potential constants in the analytical formula are evaluated from the numerical map of the adiabatic potential surface by using the linear regression method. The numerical values for 29 hexahalo complexes of the 1st row transition metals are obtained by the CNDO/2 method. Some interesting trends of parameters of such Jahn-Teller-active systems are disclosed.

Studies of the Jahn - Teller effect IV. The vibrational spectra of spin-degenerate molecules

1962 ◽  
Vol 255 (1050) ◽  
pp. 31-53 ◽  
Keyword(s):  
Raman Spectrum ◽  
Raman Spectra ◽  
Vibrational Spectra ◽  
Physical Theory ◽  
Vibronic Coupling ◽  
Infra Red ◽  
Jahn Teller ◽  
Jahn Teller Effect ◽  
Active Vibration ◽  
Degenerate States

The physical theory necessary for interpreting the vibrational spectra of spin-degenerate molecules is developed in this paper. Particular attention is paid to those molecules whose behaviour is expected to be markedly different from that of both orbitally non-degenerate molecules and those with purely spatial degeneracy. These include certain Kramers degenerate molecules, whose Raman spectra are expected to contain reverse-polarized contributions, and also tetrahedral and octahedral molecules in fourfold degenerate states. The case of a fourfold degenerate octahedral molecule is investigated in the limits of strong vibronic coupling by one of the Jahn—Teller active vibrations (e g and t 2g ). It turns out that the forbidden t 2u vibration may be infra-red active, that the Raman spectrum may contain reverse-polarized contributions and that both infra-red and Raman spectra may contain strong progressions of bands involving multiple excitations of the vibronically active vibration.

ChemInform Abstract: A Trimer Vibronic Coupling Model for Triptycene: The Jahn-Teller and Barnett Effects.

ChemInform ◽  
2010 ◽  
Vol 24 (33) ◽  
pp. no-no
Author(s):  
M. J. RILEY ◽  
A. FURLAN ◽  
H. U. GUEDEL ◽  
S. LEUTWYLER
Keyword(s):  
Coupling Model ◽  
Vibronic Coupling ◽  
Jahn Teller

Hyperconjugation In Trialkylboranes Shown By Indirect Nuclear Spin-Spin Coupling Constants. Experimental Data And Density Functional Theory (Dft) Calculations

2005 ◽  
Vol 60 (3) ◽  
pp. 259-264 ◽  
Author(s):  
Bernd Wrackmeyer ◽  
Oleg L. Tok
Keyword(s):  
Experimental Data ◽  
Dft Calculations ◽  
Density Functional ◽  
Calculated Data ◽  
Coupling Constants ◽  
Spin Coupling ◽  
Functional Theory ◽  
Spin Coupling Constants ◽  
Spin Spin Coupling ◽  
C Nmr

Trimethylborane (1), triethylborane (2), 1,3-dimethyl-1-boracyclopentane (3), 1-methyl-1- boracyclohexane (4), 9-methyl- and 9-ethyl-9-borabicyclo[3.1.1]nonane [5(Me) and 5(Et)], and 1- boraadamantane (6) were studied by 11B and 13C NMR spectroscopy with respect to coupling constants 1J(13C,11B) and 1J(13C,13C). Results of DFT calculations at the B3LYP/6-311+g(d,p) level of theory show satisfactory agreement with the experimental data. Hyperconjugation arising from C-C σ bonds adjacent to the tricoordinate boron atom is indicated, in particular for 1-boraadamantane (6), by the optimised calculated structures, and by the experimental and calculated data 1J(13C,13C). The calculated magnitude of 1J(13C,1H) for carbon atoms adjacent to boron becomes significantly smaller if the optimised structures suggest hyperconjugative effects arising from these C-H bonds

TD DFT insights into unusual properties of excited sandwich complexes: structural transformations and vibronic interactions in Rydberg-state bis(η6-benzene)chromium

2018 ◽  
Vol 20 (37) ◽  
pp. 23988-23997 ◽  
Author(s):  
Sergey Y. Ketkov ◽  
Elena A. Rychagova ◽  
Sheng-Yuan Tzeng ◽  
Wen-Bih Tzeng
Keyword(s):  
Dft Calculations ◽  
Rydberg State ◽  
Structural Transformations ◽  
Teller Effect ◽  
Sandwich Complexes ◽  
Vibronic Interactions ◽  
Td Dft ◽  
Jahn Teller ◽  
Jahn Teller Effect

TD DFT calculations reveal specific features of the Jahn–Teller effect in the lowest Rydberg p state of a prototypical sandwich molecule.

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