Pseudo-Jahn–Teller Distortion in Two-Dimensional Phosphorus: Origin of Black and Blue Phases of Phosphorene and Band Gap Modulation by Molecular Charge Transfer

Chowdhury, Chandra; Jahiruddin, Sheik; Datta, Ayan

doi:10.1021/acs.jpclett.6b00219

Cited by 76 publications

(54 citation statements)

References 63 publications

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“…For molecular systems, such instability in a high symmetric structure is accredited to pseudo Jahn–Teller (PJT) effects . In the past few years, several reports from our group have also unambiguously identified PJT distortion in silicene, germanene, phosphorene, and other two‐dimensional molecules and materials . Of them, a further proof of principle of the importance of PJT‐effects is the curious example of flattening of Silicene on Li‐atom and Ca‐atom doping in Li‐Silicene and CaSi 2 due to suppression of PJT effects.…”

Section: Introductionmentioning

confidence: 97%

Analysis of pseudo jahn–teller distortion based on natural bond orbital theory: Case study for silicene

2019

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Ground state (GS) instability of nondegenerate molecules in high symmetric structures is understood through Pseudo Jahn–Teller mixing of the electronic states through the vibronic coupling. The general approach involves setting up of a Pseudo Jahn–Teller (PJT) problem wherein one or more symmetry allowed excited states couple to the GS to create vibrational instability along a normal mode. This faces two major complications namely (1) estimating the adiabatic potential energy surfaces for the excited states which are often difficult to describe in case the excited states have charge‐transfer or multi‐excitonic (ME) character and (2) finding out how many such excited states (all satisfying the symmetry requirements for vibronic coupling) of increasing energies need to be coupled with the GS for a particular PJT problem. An analogous alternative approach presented here for the well‐known case of symmetry breaking of planar (D6h) hexasilabenzene (Si6H6) to the buckled (D3d) structure involves identifying the second‐order donor–acceptor, hyperconjugative interactions (E2i → j) that stabilize the distorted structure. Following the recent work of Nori‐Shargh and Weinhold, one observes that the orbitals involved in the vibronic coupling between the S0/Sn states and those for the donor (filled)–acceptor (empty) interactions are identical. In fact, deletion of any particular pair of E2i → j interaction creates vibrational instability in the buckled structure and as a corollary, deleting it for the planar structure removes its instability. The one‐to‐one correlation between the natural bond orbital theory and PJT theory assists in an intuitive identification of the relevant (few) excited states from a manifold of computed ones that cause symmetry breaking by vibronic coupling. © 2019 Wiley Periodicals, Inc.

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Section: Introductionmentioning

confidence: 97%

Analysis of pseudo jahn–teller distortion based on natural bond orbital theory: Case study for silicene

2019

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“…24,25 Such new 2D materials have unusual chemical bonding and stoichiometry, which could structurally mimic graphene monolayer. [26][27][28] Black phosphorous, the thermodynamically most stable allotrope of phosphorous 29 , is a layered material like graphite and is known to possess a large theoretical capacity of 2596 mAhg − 1 . 30,31 However poor cycle life and irreversible structural change limits its application as negative electrode in LIB.…”

Section: Introductionmentioning

confidence: 99%

Two-Dimensional Group IV Monochalcogenides: Anode Materials for Li-Ion Batteries

2016

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Choice of suitable electrode material is a fundamental step in Li-ion battery (LIB) to achieve enhanced performance. In the present study we have explored the feasibility of phosphorene analogs, i.e. group IV monochalcogenides (SiS, SiSe, GeS, GeSe,SnS and SnSe) monolayers to serve as anode material in LIB by density functional theory(DFT). Our exploratory study indicates lithium binds efficiently to these monolayers of which Li@SiS and Li@SiSe show appreciable stability which are comparable to phosphorene. Zero point energy corrected minimum energy pathway (MEP) for Li diffusion demonstrates high anisotropy for both SiS and SiSe with a low diffusion barrier of ~0.15eV along the zigzag direction.Inclusion of corrections due to quantum effects like the zero point energy (ZPE) and quantum mechanical tunneling (QMT) increase the diffusion rates by 6-10 % at room temperature and become increasingly significant as temperature is reduced (40-55 % increment at T=100K). The calculated theoretical capacity for SiS and SiSe are 445.7 mAhg -1 and 250.44 mAhg -1 respectively which are well above existing commercially available used anode materials. Both SiS and SiSe preserve their structural integrity upon lithiation justifying their role as host material for lithium. A semiconductor → metallic transition is observed upon full lithiation for both. All these exceptional properties including low diffusion barrier, moderate to high specific capacity, low open circuit voltage (OCV), small volume change and good electrical conductivity, suggest that monolayer SiS and SiSe could serve as a promising electrode material in LIB.

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“…For example, the Jahn–Teller distortion has been widely used to explain spontaneous symmetry breaking of molecular systems when spatially degenerate electronic ground states exist in the undistorted structure. While graphene is mostly flat, pseudo‐Jahn–Teller distortions have been invoked to understand the formation of highly puckered 2D materials including black and blue phosphorene, silicene, and germanene, where the electronic states are nondegenerate but possess small splitting and strong vibronic coupling . On the other hand, the larger gaps between the ground state and higher states in graphene suppress the instability toward distortion .…”

Section: Surface and Interface Phenomenamentioning

confidence: 99%

Interface Characterization and Control of 2D Materials and Heterostructures

2018

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2D materials and heterostructures have attracted significant attention for a variety of nanoelectronic and optoelectronic applications. At the atomically thin limit, the material characteristics and functionalities are dominated by surface chemistry and interface coupling. Therefore, methods for comprehensively characterizing and precisely controlling surfaces and interfaces are required to realize the full technological potential of 2D materials. Here, the surface and interface properties that govern the performance of 2D materials are introduced. Then the experimental approaches that resolve surface and interface phenomena down to the atomic scale, as well as strategies that allow tuning and optimization of interfacial interactions in van der Waals heterostructures, are systematically reviewed. Finally, a future outlook that delineates the remaining challenges and opportunities for 2D material interface characterization and control is presented.

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Pseudo-Jahn–Teller Distortion in Two-Dimensional Phosphorus: Origin of Black and Blue Phases of Phosphorene and Band Gap Modulation by Molecular Charge Transfer

Cited by 76 publications

References 63 publications

Analysis of pseudo jahn–teller distortion based on natural bond orbital theory: Case study for silicene

Analysis of pseudo jahn–teller distortion based on natural bond orbital theory: Case study for silicene

Two-Dimensional Group IV Monochalcogenides: Anode Materials for Li-Ion Batteries

Interface Characterization and Control of 2D Materials and Heterostructures

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