Dipole-bound anions of highly polar molecules: Ethylene carbonate and vinylene carbonate

Hammer, Nathan I.; Hinde, Robert J.; Compton, R. N.; Diri, Kadir; Jordan, Kenneth D.; Radisic, Dunja; Stokes, Sarah T.; Bowen, Kit H.

doi:10.1063/1.1629669

Cited by 66 publications

(56 citation statements)

References 39 publications

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“…In fact, EC − anion has been observed experimentally. 70 The difference between LUMO/HOMO orbitals of EC − in gas and solution phases was shown in a later study by Yu et al 60 Under the effect of a continuum solvent model, EC can be reduced via one-electron and possibly twoelectron reactions in the solution. By computing the EC reduction pathways with Li + and increasing numbers of EC in Li + (EC) n , Wang et al 15 confirmed the currently generally accepted two-step reduction pathways on the surface that Li + (EC) n is initially reduced to an ion-pair intermediate undergoing homolytic C-O bond cleavage, giving a radical anion coordinated with Li + .…”

Section: Ec Solvent Decomposition Mechanismmentioning

confidence: 99%

Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries

et al. 2018

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A passivation layer called the solid electrolyte interphase (SEI) is formed on electrode surfaces from decomposition products of electrolytes. The SEI allows Li + transport and blocks electrons in order to prevent further electrolyte decomposition and ensure continued electrochemical reactions. The formation and growth mechanism of the nanometer thick SEI films are yet to be completely understood owing to their complex structure and lack of reliable in situ experimental techniques. Significant advances in computational methods have made it possible to predictively model the fundamentals of SEI. This review aims to give an overview of state-of-the-art modeling progress in the investigation of SEI films on the anodes, ranging from electronic structure calculations to mesoscale modeling, covering the thermodynamics and kinetics of electrolyte reduction reactions, SEI formation, modification through electrolyte design, correlation of SEI properties with battery performance, and the artificial SEI design. Multiscale simulations have been summarized and compared with each other as well as with experiments. Computational details of the fundamental properties of SEI, such as electron tunneling, Li-ion transport, chemical/mechanical stability of the bulk SEI and electrode/(SEI/) electrolyte interfaces have been discussed. This review shows the potential of computational approaches in the deconvolution of SEI properties and design of artificial SEI. We believe that computational modeling can be integrated with experiments to complement each other and lead to a better understanding of the complex SEI for the development of a highly efficient battery in the future.

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Section: Ec Solvent Decomposition Mechanismmentioning

confidence: 99%

Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries

et al. 2018

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“…DBS was predicted to exist for neutral molecules with sufficiently large dipole moments (>2.5D) [130][131][132][133] and had been observed, [134][135][136][137][138] usually with very low binding energies. Excited DBSs near the detachment thresholds of anions were observed by Brauman and co-workers in photodetachment cross sections.…”

Section: A Pes Of Phenoxide At Room Temperature and Observation Of Dmentioning

confidence: 99%

Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

Wang

2015

The Journal of Chemical Physics

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Electrospray ionization (ESI) has become an essential tool in chemical physics and physical chemistry for the production of novel molecular ions from solution samples for a variety of spectroscopic experiments. ESI was used to produce free multiply-charged anions (MCAs) for photoelectron spectroscopy (PES) in the late 1990 s, allowing many interesting properties of this class of exotic species to be investigated. Free MCAs are characterized by strong intramolecular Coulomb repulsions, which create a repulsive Coulomb barrier (RCB) for electron emission. The RCB endows many fascinating properties to MCAs, giving rise to meta-stable anions with negative electron binding energies. Recent development in the PES of MCAs includes photoelectron imaging to examine the influence of the RCB on the electron emission dynamics, pump-probe experiments to examine electron tunneling through the RCB, and isomer-specific experiments by coupling PES with ion mobility for biological MCAs. The development of a cryogenically cooled Paul trap has led to much better resolved PE spectra for MCAs by creating vibrationally cold anions from the room temperature ESI source. Recent advances in coupling the cryogenic Paul trap with PE imaging have allowed high-resolution PE spectra to be obtained for singly charged anions produced by ESI. In particular, the observation of dipole-bound excited states has made it possible to conduct vibrational autodetachment spectroscopy and resonant PES, which yield much richer vibrational spectroscopic information for dipolar free radicals than traditional PES.

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“…[5][6][7][8][9][10] Negative ions with dipolar molecular cores can have excited dipole-bound states (DBSs) near the detachment threshold, analogous to Rydberg states in neutral molecules. DBSs in excited anions were first observed as resonances in photodetachment crosssections.…”

mentioning

confidence: 99%

Observation of Mode‐Specific Vibrational Autodetachment from Dipole‐Bound States of Cold Anions

Liu¹,

Ning²,

Huang³

et al. 2013

Angew Chem Int Ed

111

191

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Molecules with sufficiently large dipole moments were predicted to form weakly bound negative ions in the dipolar field [1][2][3][4] and such dipole-bound anions have been observed and characterized experimentally. [5][6][7][8][9][10] Negative ions with dipolar molecular cores can have excited dipole-bound states (DBSs) near the detachment threshold, analogous to Rydberg states in neutral molecules. DBSs in excited anions were first observed as resonances in photodetachment crosssections. [11][12][13] Ultrahigh resolution spectroscopy has been reported on excited DBSs of a number of anions near their detachment threshold by autodetachment. [14][15][16] The theory for autoionization from Rydberg states was first developed by Berry, [17] who predicted a Dv = À1 vibrational propensity rule, that is, the Rydberg state undergoes a vibrational relaxation by one vibrational quantum in the molecular core during autoionization, in which the vibrational energy is transferred to the Rydberg electron. The Dv = À1 propensity rule has been observed in autoionization of numerous molecules [18][19][20] and mode-specific autoionization has been observed by photoelectron spectroscopy, [21] in which the kinetic energies of the outgoing electrons are measured. The same Dv = À1 propensity rule should apply in autodetachment from DBSs of excited anions [22] and has been inferred in previous studies.[ 13,16] However, the electron kinetic energies of the outgoing autodetached electrons from the excited DBSs have not been measured by electron spectroscopy.All prior studies of DBSs in excited anions are dominated by rotational effects [23,24] and pure vibrational autodetachment from DBSs has not been reported, even though vibrational autodetachment has been observed in weakly bound anions and has been used effectively as a spectroscopic tool for anions. [25][26][27] Here we report the direct observation of pure vibrational autodetachment from DBSs of cryogenically cooled phenoxide anions using high-resolution photoelectron imaging. Autodetachment from eight vibrational levels of the DBS in optically exited phenoxide anions are observed and the Dv = À1 propensity rule is found to be strictly obeyed.

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Dipole-bound anions of highly polar molecules: Ethylene carbonate and vinylene carbonate

Cited by 66 publications

References 39 publications

Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries

Review on modeling of the anode solid electrolyte interphase (SEI) for lithium-ion batteries

Perspective: Electrospray photoelectron spectroscopy: From multiply-charged anions to ultracold anions

Observation of Mode‐Specific Vibrational Autodetachment from Dipole‐Bound States of Cold Anions

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