Raman spectra from <i>ab initio</i> molecular dynamics and its application to liquid <i>S</i>-methyloxirane

Luber, Sandra; Iannuzzi, Marcella; Hutter, Jürg

doi:10.1063/1.4894425

Cited by 80 publications

(103 citation statements)

References 93 publications

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“…The prediction of infrared (IR) and Raman intensities, however, requires additional information about dipole moments and polarizabilities along the trajectory. An established approach to obtain dipole moments of individual molecules in the simulation is the maximally localized Wannier function scheme, [2][3][4][5][6][7][8][9][10][11][12] where a set of localized Wannier orbitals is created from the Kohn-Sham orbitals inherently available in each timestep. The position expectation values of these localized orbitals are taken as the locations of the electrons, which can be assigned to the individual molecules by a minimum distance criterion.…”

Section: Introductionmentioning

confidence: 99%

Voronoi dipole moments for the simulation of bulk phase vibrational spectra

Thomas

Brehm

Kirchner

2015

Phys. Chem. Chem. Phys.

110

174

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We present the Voronoi tessellation of electron density data to obtain molecular dipole moments in bulk phase ab initio molecular dynamics simulations for the calculation of vibrational spectra. Opposed to the established scheme of maximally localized Wannier functions, this approach does not rely on computationally demanding localization procedures. Nevertheless, we show at the examples of methanol, benzene, and phenol that it provides infrared and Raman spectra of similar quality and is even superior in specific cases like the Raman spectra of benzene and phenol. We have also applied the Voronoi method to a mixture of the ionic liquid 1-ethyl-3-methylimidazolium acetate with water, and show that it is advantageous in systems with significant charge transfer.

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Section: Introductionmentioning

confidence: 99%

Voronoi dipole moments for the simulation of bulk phase vibrational spectra

Thomas

Brehm

Kirchner

2015

Phys. Chem. Chem. Phys.

110

174

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“…Molecular dynamics (MD) simulations are a powerful tool to investigate the nature and dynamics of the strong interactions between the anions and cations, as well as between the anions themselves through the formation of hydrogen bonds in an ensemble of molecules. [11,23,24] We therefore performed a Born-Oppenheimer MD simulation with Kohn-Sham density functional theory as the electronic structure method (DFT-MD; see Supporting Information for more information). The focus of the analysis of the DFT-MD trajectory lay on the change of dihedral angles that describe the ions conformation and are therefore accountable for changes in the ROA spectrum.…”

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confidence: 99%

Symmetry Breaking in Chiral Ionic Liquids Evidenced by Vibrational Optical Activity

et al. 2016

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Ionic liquids (ILs) are receiving increasing interest for their use in synthetic laboratories and industry. Being composed of charged entities, they show a complex and widely unexplored dynamic behavior. Chiral ionic liquids (CILs) have a high potential as solvents for use in asymmetric synthesis. Chiroptical methods, owing to their sensitivity towards molecular conformation, offer unique possibilities to study the structure of these chiral ionic liquids. Raman optical activity proved particularly useful to study ionic liquids composed of amino acids and the achiral 1-ethyl-3-methylimidazolium counterion. We could substantiate, supported by selected theoretical methods, that the achiral counterion adopts an overall chiral conformation in the presence of chiral amino acid ions. These findings suggest that in the design of chiral ionic liquids for asymmetric synthesis, the structure of the achiral counter ion also has to be carefully considered.

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“…This liquid was simulated with a periodic cubic box containing 20 subsets of (S)-methyloxirane molecules at a density of 0.830 g/l. 130,131 Again, WC/Loc was found to be minor, namely, 4.0% (mSD: 2.9%), and Loc/WC-nE somewhat larger (5.0%; mSD: 3.5%). The mean relative difference between WC-Dip(E) and WC-Dip(nE) was 2.5% (mSD: 2.9%).…”

Section: A Liquidsmentioning

confidence: 99%

Local electric dipole moments for periodic systems via density functional theory embedding

Luber

2014

The Journal of Chemical Physics

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We describe a novel approach for the calculation of local electric dipole moments for periodic systems. Since the position operator is ill-defined in periodic systems, maximally localized Wannier functions based on the Berry-phase approach are usually employed for the evaluation of local contributions to the total electric dipole moment of the system. We propose an alternative approach: within a subsystemdensity functional theory based embedding scheme, subset electric dipole moments are derived without any additional localization procedure, both for hybrid and non-hybrid exchange-correlation functionals. This opens the way to a computationally efficient evaluation of local electric dipole moments in (molecular) periodic systems as well as their rigorous splitting into atomic electric dipole moments. As examples, Infrared spectra of liquid ethylene carbonate and dimethyl carbonate are presented, which are commonly employed as solvents in Lithium ion batteries. We describe a novel approach for the calculation of local electric dipole moments for periodic systems. Since the position operator is ill-defined in periodic systems, maximally localized Wannier functions based on the Berry-phase approach are usually employed for the evaluation of local contributions to the total electric dipole moment of the system. We propose an alternative approach: within a subsystem-density functional theory based embedding scheme, subset electric dipole moments are derived without any additional localization procedure, both for hybrid and non-hybrid exchangecorrelation functionals. This opens the way to a computationally efficient evaluation of local electric dipole moments in (molecular) periodic systems as well as their rigorous splitting into atomic electric dipole moments. As examples, Infrared spectra of liquid ethylene carbonate and dimethyl carbonate are presented, which are commonly employed as solvents in Lithium ion batteries. © 2014 AIP Publishing LLC. [http://dx

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Raman spectra from ab initio molecular dynamics and its application to liquid S-methyloxirane

Cited by 80 publications

References 93 publications

Voronoi dipole moments for the simulation of bulk phase vibrational spectra

Voronoi dipole moments for the simulation of bulk phase vibrational spectra

Symmetry Breaking in Chiral Ionic Liquids Evidenced by Vibrational Optical Activity

Local electric dipole moments for periodic systems via density functional theory embedding

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