X-ray diffraction data for 1-alkyl-3-methylimidazolium bis{(trifluoromethyl)sulfonyl}amides are reported as a function of the length alkyl chain on imidazolium ring. The measured patterns have been compared with theoretical calculated (from geometries obtained) molecular dynamics simulations. This provides detailed description (at atomistic level) morphology in liquid state these salts, highlighting role played by length. An analysis behavior hydrogen bonds that formed between acidic protons...

We present an analysis of gas-phase structures small clusters n-alkylammonium nitrates (ethyl, propyl, and butyl) together with vibrational Raman spectroscopy their respective liquid phases. The assignment interpretation the resonant frequencies have been performed by comparison high-quality ab initio (DFT) computations. theoretical spectra are in excellent agreement measured ones allow almost all spectral features. A careful electronic structure compounds has provided additional information...

We present a quantum mechanical study of the reaction F+D2 at ultracold temperatures based on potential energy surface Stark and Werner. The cross section low energies is controlled by tunneling through activation barrier, mechanism that favored long duration collision those energies. Differences are found in behavior reactive compared to for F+H2, due changed mass zero point energy. A new feature detected probabilities attributed Feshbach resonance corresponding metastable state exit channel.

The first experimental study of the X-ray absorption spectrum (XAS) allyl free radical, CH2CHCH2, is reported. A supersonic He seeded beam hyperthermal radicals was crossed by a high resolution synchrotron radiation (SR) in focus 3D ion momentum imaging time-of-flight (TOF) spectrometer to investigate soft and fragmentation processes. XAS, recorded as Total-Ion-Yield (TIY), dominated C1s electron excitations from either central carbon atom, CC, or two terminal atoms, CT, frontier orbitals,...

In this study, we discuss the performance of classical molecular dynamics in predicting experimental X-ray diffraction patterns liquid ethylammonium nitrate (one simplest protic room-temperature ionic showing amphiphilic behavior) and its hydroxy derivative (2-ethanolammonium nitrate, 2-HOEAN). Newly recorded energy-dispersive structure factors are compared with corresponding quantities extracted from simulations. Other useful theoretical indicators used as a probe local title liquids. We...

The combination of amino acid anions with the choline cation gives origin to a new and potentially important class organic ionic liquids that might represent viable bio-compatible alternative respect traditional ones. We present here detailed study bulk phase prototype system composed simplest (alanine) anion cation, based on ab initio classical molecular dynamics. Theoretical findings have been validated by comparing accurate experimental X-ray diffraction data infrared spectra. find...

We present a computational analysis of the short-range structure three protic ionic liquids based on strong organic acids: trifluoracetate, methanesulfonate, and triflate triethylammonium. Accurate ab initio computations carried out gas-phase dimers show that protonation triethylamine is spontaneous. have identified anion-cation binding motif due to presence hydrogen bond electrostatic interactions. The strength magnitude energy decrease in order trifluoroacetate ≳ methanesulfonate >...

The behaviour of reactive scattering at ultracold temperatures is explored by calculating the real and imaginary parts length for reaction F with a molecule composed pair pseudo-hydrogen atoms arbitrary mass. origin low energy feature in cross section H2 its absence D2 investigated. Close-coupling calculations matrix show that F–H2 arises from presence virtual state associated van der Waals well entrance channel responsible enhanced zero temperature rate coefficient reaction. For mass about...

We present an analysis of the structure monomethylammonium nitrate (MMAN) compound. Vibrational Raman spectroscopy and X-ray powder diffraction have been used to characterize bulk phases MMAN, assignment resonant frequencies has performed by ab initio (DFT) computations on small clusters The theoretical spectra are in excellent agreement with experimental ones provide a means which interpretation hydrogen-bonding network that exists such compound can be analyzed. In particular, we found...

The combination of amino acids in their deprotonated and thus anionic form with a choline cation gives origin to new potentially important class organic ionic compounds. A series such neutral ion pairs has been investigated by first principle methods. results reveal intriguing structural motives as well regular patterns the charge distribution predict number vibrational optical properties that could guide experimental investigation these replacement its phosphocholine analogue causes...

Abstract This study explores the properties of aprotic electrolytes via application experimental methods, including nuclear magnetic resonance spectroscopy and electrochemical techniques, along with molecular dynamic modeling. The aim is to provide a quantitative description physico‐chemical two well‐established (case studies), each exhibiting significantly distinct dielectric properties: LiTFSI (Lithium bis(trifluoromethanesulfonyl)imide) solution in dimethyl sulfoxide (DMSO, constant...

In this paper, we present a molecular dynamics study of the structural and dynamical properties γ-valerolactone (GVL) both as standalone solvent in electrolyte formulations for electrochemistry applications. This involves developing new parameterization polarizable forcefield applying it to simulate pure GVL selected salt solutions. The was validated with experimental bulk data quantum mechanical calculations, excellent agreement obtained cases. Specifically, two 1M solutions lithium...

A study on the amino acid‐mediated intramolecular cyclization of diketoaldehyde 2 to form bicyclic ketocarbaldehyde 1, a potentially useful intermediate in synthesis some polycyclic diterpenes, is hereafter presented. This exhibits peculiar enantio‐selectivity if compared similar cyclizations due its product being (S)‐enantiomer when using d‐amino acids. Our findings reveal that transformation proceeds through two irreversible steps: and subsequent dehydration process. The reaction...

Three-dimensional potential energy surfaces (PESs) have been computed, and numerically fitted, for the two lowest electronic states of LiH2+ system, which are importance astrophysically relevant LiH++H→Li++H2 LiH+H+→Li+H2+ exoergic reactions. We extend recently computed 11 000 multi reference valence bond ab initio values [Martinazzo et al., Chem. Phys. 287, 335 (2003)] with 600 multireference configuration interaction calculations complete active self-consistent field functions a large...

Variational Monte Carlo and diffusion calculations have been carried out for cations such as Li+, Na+, K+ dopants of small helium clusters over a range cluster sizes up to about 12 solvent atoms. The interaction has modeled through sum-of-potential picture that disregards higher order effects beyond atom-atom atom-ion contributions. latter were obtained from highly correlated ab initio broad interatomic distances. This study focuses on two the most striking features microsolvation in quantum...

In this work, we report molecular dynamics simulations of the bulk liquid phase geminal di-imidazolium bis(trifluoromethylsulfonyl)imide ionic liquids. We characterize a few interesting features local structure in phase, and make comparison both with gas structures monoimidazolic counterparts. analyze detail diffraction properties these fluids by simulating X-ray neutron scattering factors on long-range structural order that seems to also arise one compounds.

We present an analysis of the liquid and a small isolated cluster n-ethyl ammonium nitrate based on “first principles” molecular dynamics. discover that peculiar properties ionic liquids make such compounds ideal candidates for analysis. have been able to characterize some important features structure we validated our simulations by comparing findings with experimental vibrational spectra phase. Theoretical spectra, which remarkable agreement measurements, besides assignment main features,...

We explore the structure of a series protic Ionic Liquids based on choline cation and amino acid anions. In series, length branching alkyl chain varies. Ab initio molecular dynamics, X-ray diffraction measurements, infrared spectra have been used to provide reliable picture short-range short-time dynamic process that characterize fluids. put special emphasis peculiar complicated network hydrogen bonds stem from amphoteric nature anion moiety. The use ab dynamics allows us calculate "exact"...

A combined experimental/theoretical approach has been used to investigate the role of water in modifying microscopic interactions characterizing optical response 1-butyl-ammonium nitrate (BAN) solutions. Raman spectra, dominated by signal from protic ionic liquid, were collected as a function content, and corresponding spatial organization couples, well their local arrangement with molecules, was studied exploiting classical molecular dynamics calculations. High quality spectroscopic data,...

Silver nanoparticles (AgNPs) functionalized with an organometallic bifunctional thiol containing Pt(ii) centers, generated in situ from trans-trans-[thioacetyl-bistributylphosphine-diethynylbiphenyl-diplatinum(ii)], were synthesized different sulphur/metal molar ratios (i.e. AgNPs-1 and AgNPs-2) the aim to obtain nanosystems of mean size self-organization behaviour. AgNPs spontaneously self-assemble, giving rise 2D networks, as previously assessed. In this work a deeper insight into...

We have explored by means of ab initio molecular dynamics the homologue series 11 different ionic liquids based on combination cholinium cation with deprotonated amino acid anions. present a structural analysis liquid states these compounds as revealed accurate computations forces. highlight persistent motifs that see couple basic building block whereby strong hydrogen bonding network substantially determines short range behavior bulk state. Other minor docking features interaction are also...

Abstract Herein, the design of novel and safe electrolyte formulations for high‐voltage Ni‐rich cathodes is reported. The solvent mixture comprising 1,1,2,2‐tetraethoxyethane propylene carbonate not only displays good transport properties, but also greatly enhances overall safety cell thanks to its low flammability. influence conducting salts, that is, lithium bis(trifluoromethanesulfonyl)imide (LiTFSI) bis(fluorosulfonyl)imide (LiFSI), additives bis(oxalato)borate (LiBOB)...