Solvation Structure and Transport of Acidic Protons in Ionic Liquids:  A First-principles Simulation Study

Pópolo, Mario G. Del; Kohanoff, Jorge; Lynden‐Bell, R. M.

doi:10.1021/jp0602326

Cited by 57 publications

(60 citation statements)

References 28 publications

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“…͑8͒.͔ The system studied here is ͓ClHCl͔ − . This has been the subject of many experimental and theoretical studies 42,[103][104][105][106][107][108][109] and contains a shared proton undergoing excursions between donor-acceptor moieties. It has also been seen in previous studies that the system presents a challenge on account of significant electron-nuclear coupling.…”

Section: -10mentioning

confidence: 99%

Quantum wavepacket ab initio molecular dynamics: Generalizations using an extended Lagrangian treatment of diabatic states coupled through multireference electronic structure

Iyengar

2010

The Journal of Chemical Physics

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We present a generalization to our previously developed quantum wavepacket ab initio molecular dynamics ͑QWAIMD͒ method by using multiple diabatic electronic reduced single particle density matrices, propagated within an extended Lagrangian paradigm. The Slater determinantal wavefunctions associated with the density matrices utilized may be orthogonal or nonorthogonal with respect to each other. This generalization directly results from an analysis of the variance in electronic structure with quantum nuclear degrees of freedom. The diabatic electronic states are treated here as classical parametric variables and propagated simultaneously along with the quantum wavepacket and classical nuclei. Each electronic density matrix is constrained to be N-representable. Consequently two sets of new methods are derived: extended Lagrangian-QWAIMD ͑xLag-QWAIMD͒ and diabatic extended Lagrangian-QWAIMD ͑DxLag-QWAIMD͒. In both cases, the instantaneous potential energy surface for the quantum nuclear degrees of freedom is constructed from the diabatic states using an on-the-fly nonorthogonal multireference formalism. By introducing generalized grid-based electronic basis functions, we eliminate the basis set dependence on the quantum nucleus. Subsequent reuse of the two-electron integrals during the on-the-fly potential energy surface computation stage yields a substantial reduction in computational costs. Specifically, both xLag-QWAIMD and DxLag-QWAIMD turn out to be about two orders of magnitude faster than our previously developed time-dependent deterministic sampling implementation of QWAIMD. Energy conservation properties, accuracy of the associated potential surfaces, and vibrational properties are analyzed for a family of hydrogen bonded systems.

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Section: -10mentioning

confidence: 99%

Quantum wavepacket ab initio molecular dynamics: Generalizations using an extended Lagrangian treatment of diabatic states coupled through multireference electronic structure

Iyengar

2010

The Journal of Chemical Physics

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“…Notably, there exists a large number of ionic liquids that differ in their anion and cation composition which offers tunable functionalities and a broad applicability 16,17 . Specifically the ionic dissociation behavior and the corresponding transport properties of ILs have been studied by computer simulations and experiments in a series of publications 11,12,14,[18][19][20][21][22][23][24][25][26][27][28][29][30] . Nowadays, ionic liquids have attracted a broad interest in the usage as solvents due to their desirable, less hazardous properties compared to other media 5,7,31 .…”

Section: Introductionmentioning

confidence: 99%

Solvent effects of 1-ethyl-3-methylimidazolium acetate: solvation and dynamic behavior of polar and apolar solutes

Lesch

Heuer

Holm

et al. 2015

Phys. Chem. Chem. Phys.

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We study the solvation properties of the ionic liquid 1-ethyl-3-methylimidazolium acetate ([EMIM](+)[ACE](-)) and the resulting dynamic behavior for differently charged model solutes at room temperature via atomistic molecular dynamics (MD) simulations of 300 ns length and 200 ns equilibration time. The solutes are simple model spheres which are either positively or negatively charged with a valency of one, or uncharged. The numerical findings indicate a distinct solvation behavior with the occurrence of well-pronounced solvation shells whose composition significantly depends on the charge of the solute. All the results of our simulations evidence the existence of a long-range perturbation effect in presence of the solutes. Our findings validate the dominance of electrostatic interactions with regard to unfavorable entropic ordering effects which elucidates the enthalpic character of the solvation process in ionic liquids for charged solutes.

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“…Popolo et al24 simulated the dissolution and solvation of HCl in the ionic liquid [C 1 mim]Cl, and observed the rapid formation of the anion [HCl 2 ] − , rather than dissociation. Several other works have focussed on the behaviour of Bronsted acids in RTILs [25][26][27].…”

mentioning

confidence: 99%

Measuring the solubility of benzoic acid in room temperature ionic liquids using chronoamperometric techniques

Silvester

Streeter

et al. 2008

J of Physical Organic Chem

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The electrochemical reduction of benzoic acid (BZA) has been studied at platinum microelectrodes (10 µm and 2 µm diameter) in acetonitrile (MeCN) and six room temperature ionic liquids (RTILs): [C 2 mim][NTf 2 ], [C 4 mpyrr][NTf 2 ], [C 4 mim][OTf], [C 4 mim][NO 3 ] and [C 4 mim][PF 6 ] (where [C n mim] + = 1-alkyl-3-methylimidazolium, [NTf 2 ] − = bis(trifluoromethylsulfonyl)imide, [C 4 mpyrr] + = N-butyl-N-methylpyrrolidinium, [OTf] − = trifluoromethlysulfonate, [NO 3 ] − = nitrate and [PF 6 ] − = hexafluorophosphate). Based on the theoretical fitting to experimental chronoamperometric transients in [C 4 mpyrr][NTf 2 ] and MeCN at several concentrations and on

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Solvation Structure and Transport of Acidic Protons in Ionic Liquids: A First-principles Simulation Study

Cited by 57 publications

References 28 publications

Quantum wavepacket ab initio molecular dynamics: Generalizations using an extended Lagrangian treatment of diabatic states coupled through multireference electronic structure

Quantum wavepacket ab initio molecular dynamics: Generalizations using an extended Lagrangian treatment of diabatic states coupled through multireference electronic structure

Solvent effects of 1-ethyl-3-methylimidazolium acetate: solvation and dynamic behavior of polar and apolar solutes

Measuring the solubility of benzoic acid in room temperature ionic liquids using chronoamperometric techniques

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