Divalent-dopant criterion for the suppression of Jahn-Teller distortion in Mn oxides: First-principles calculations and x-ray absorption spectroscopy measurements for Co inLiMnO2

We report a theoretical investigation and elucidation of the x-ray absorption spectra of neutral benzene and of the benzene cation. The generation of the cation by multiphoton ultraviolet (UV) ionization as well as the measurement of the carbon K-edge spectra of both species using a table-top high-harmonic generation (HHG) source are described in the companion experimental paper [M. Epshtein et al., J. Phys. Chem. A., submitted. Available on ChemRxiv]. We show that the 1sC -> pi transition serves as a sensitive signature of the transient cation formation, as it occurs outside of the spectral window of the parent neutral species. Moreover, the presence of the unpaired (spectator) electron in the pi-subshell of the cation and the high symmetry of the system result in significant differences relative to neutral benzene in the spectral features associated with the 1sC ->pi* transitions. High-level calculations using equation-of-motion coupled-cluster theory provide the interpretation of the experimental spectra and insight into the electronic structure of benzene and its cation. The prominent split structure of the 1sC -> pi* band of the cation is attributed to the interplay between the coupling of the core -> pi* excitation with the unpaired electron in the pi-subshell and the Jahn-Teller distortion. The calculations attribute most of the splitting (~1-1.2 eV) to the spin coupling, which is visible already at the Franck-Condon structure, and estimate the additional splitting due to structural relaxation to be around ~0.1-0.2 eV. These results suggest that x-ray absorption with increased resolution might be able to disentangle electronic and structural aspects of the Jahn-Teller effect in benzene cation.

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New Insights on the Reversible Lithiation Mechanism of TiO2(B) by Operando X-ray Absorption Spectroscopy and X-ray Diffraction Assisted by First-Principles Calculations

The Journal of Physical Chemistry C ◽

10.1021/jp507574e ◽

2014 ◽

Vol 118 (47) ◽

pp. 27210-27218 ◽

Cited By ~ 17

Author(s):

Marcus Fehse ◽

Mouna Ben Yahia ◽

Laure Monconduit ◽

Frédéric Lemoigno ◽

Marie-Liesse Doublet ◽

...

Keyword(s):

Absorption Spectroscopy ◽

First Principles ◽

First Principles Calculations ◽

X Ray Diffraction ◽

X Ray ◽

X Ray Absorption

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Iodate in calcite and vaterite: Insights from synchrotron X-ray absorption spectroscopy and first-principles calculations

Geochimica et Cosmochimica Acta ◽

10.1016/j.gca.2016.11.032 ◽

2017 ◽

Vol 198 ◽

pp. 218-228 ◽

Cited By ~ 28

Author(s):

J. Podder ◽

J. Lin ◽

W. Sun ◽

S.M. Botis ◽

J. Tse ◽

...

Keyword(s):

Absorption Spectroscopy ◽

First Principles ◽

First Principles Calculations ◽

X Ray ◽

X Ray Absorption

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Determining Atomic-Scale Structure and Composition of Organo-Lead Halide Perovskites by Combining High-Resolution X-ray Absorption Spectroscopy and First-Principles Calculations

ACS Energy Letters ◽

10.1021/acsenergylett.7b00182 ◽

2017 ◽

Vol 2 (5) ◽

pp. 1183-1189 ◽

Cited By ~ 11

Author(s):

Walter S. Drisdell ◽

Linn Leppert ◽

Carolin M. Sutter-Fella ◽

Yufeng Liang ◽

Yanbo Li ◽

...

Keyword(s):

High Resolution ◽

Absorption Spectroscopy ◽

First Principles ◽

Scale Structure ◽

Atomic Scale ◽

First Principles Calculations ◽

X Ray ◽

Halide Perovskites ◽

X Ray Absorption ◽

Lead Halide

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Characterization of Polysulfide Radicals Present in an Ether-Based Electrolyte of a Lithium-Sulfur Battery During Initial Discharge Using In Situ X-Ray Absorption Spectroscopy Experiments and First-Principles Calculations

Advanced Energy Materials ◽

10.1002/aenm.201500285 ◽

2015 ◽

Vol 5 (16) ◽

pp. 1500285 ◽

Cited By ~ 70

Author(s):

Kevin H. Wujcik ◽

Tod A. Pascal ◽

C. D. Pemmaraju ◽

Didier Devaux ◽

Wayne C. Stolte ◽

...

Keyword(s):

Absorption Spectroscopy ◽

First Principles ◽

First Principles Calculations ◽

X Ray ◽

Initial Discharge ◽

Sulfur Battery ◽

X Ray Absorption ◽

Lithium Sulfur

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First-principles calculations on the Jahn–Teller distortion in layered LiMnO2

Journal of Power Sources ◽

10.1016/j.jpowsour.2005.10.044 ◽

2006 ◽

Vol 158 (2) ◽

pp. 1394-1400 ◽

Cited By ~ 14

Author(s):

Zu-Fei Huang ◽

Xing Meng ◽

Chun-Zhong Wang ◽

Yuan Sun ◽

Gang Chen

Keyword(s):

First Principles ◽

First Principles Calculations ◽

Teller Distortion ◽

Jahn Teller ◽

Layered Limno2 ◽

Jahn Teller Distortion

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Vacancy induced Jahn–Teller distortion in silicon and its influence to the electronic structure

Modern Physics Letters B ◽

10.1142/s0217984915501365 ◽

2015 ◽

Vol 29 (24) ◽

pp. 1550136

Author(s):

Shuying Zhong ◽

Xueling Lei ◽

Lang Zhou

Keyword(s):

Electronic Structure ◽

Charge Density ◽

First Principles ◽

Electronic Structures ◽

Crystalline Silicon ◽

First Principles Calculations ◽

Teller Distortion ◽

Jahn Teller ◽

The Difference ◽

Jahn Teller Distortion

Atomic and electronic structures of monovacancy (V1), divacancy (V2) and ring hexavacancy (V6) in crystalline silicon are studied using first-principles calculations in periodic supercells. Our results show that the V6 defect is the most stable among V1, V2 and V6 defects, and the V2-RB structure is a little more stable than the V2-LP structure due to lower vacancy formation energy. Furthermore, it is found that both V1 and V2 undergo the Jahn–Teller (JT) distortion while V6 does not. As a result, V1 and V2 have deep levels in the gap which mainly come from the neighboring atoms to vacancy. V6 has tailing bands in the gap, and so has a more stable electronic structure than V1 and V2. In addition, the JT distortion also reflects in the band decomposed charge density and the difference charge density.

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