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Journal of Chemical Physics

Mahsa Ebadi, Daniel Brandell, C Moyses Araujo
An important feature in Li batteries is the formation of a solid electrolyte interphase (SEI) on the surface of the anode. This film can have a profound effect on the stability and the performance of the device. In this work, we have employed density functional theory combined with implicit solvation models to study the inner layer of SEI formation from the reduction of common organic carbonate electrolyte solvents (ethylene carbonate, propylene carbonate, dimethyl carbonate, and diethyl carbonate) on a Li metal anode surface...
November 28, 2016: Journal of Chemical Physics
Eszter Makkos, Andrew Kerridge, Jonathan Austin, Nikolas Kaltsoyannis
Density functional theory (DFT) at the generalised gradient approximation level is employed within the periodic electrostatic embedded cluster method (PEECM) to model the brucite (0001) surface. Three representative studies are then used to demonstrate the reliability of the PEECM for the description of the interactions of various ionic species with the layered Mg(OH)2 structure, and its performance is compared with periodic DFT, an approach known to be challenging for the adsorption of charged species. The adsorption energies of a series of s block cations, including Sr(2+) and Cs(+) which are known to coexist with brucite in nuclear waste storage ponds, are well described by the embedded cluster model, provided that basis sets of triple-zeta quality are employed for the adsorbates...
November 28, 2016: Journal of Chemical Physics
H R Larsson, B Hartke, D J Tannor
We present an efficient implementation of dynamically pruned quantum dynamics, both in coordinate space and in phase space. We combine the ideas behind the biorthogonal von Neumann basis (PvB) with the orthogonalized momentum-symmetrized Gaussians (Weylets) to create a new basis, projected Weylets, that takes the best from both methods. We benchmark pruned time-dependent dynamics using phase-space-localized PvB, projected Weylets, and coordinate-space-localized DVR bases, with real-world examples in up to six dimensions...
November 28, 2016: Journal of Chemical Physics
Yu Xia, Zhibing Li
To understand laser-assisted field evaporation of semiconductors and insulators at the microscopic level, we study the time evolution of the electronic and atomic structure of a MgO cluster in high electrostatic fields subjected to strong laser pulses. We find that the critical laser intensity for evaporation decreases linearly as the electrostatic field strength increases. The optical absorption enhancement in high electrostatic field is confirmed by the redshift of the optical absorption spectra, the reduction of the energy gap, and the increase of the absorption cross section...
November 28, 2016: Journal of Chemical Physics
Phwey S Gil, Daniel J Lacks
Here we study the relationship between a surfactant's molecular shape and its tendency to partition to the interface in ethanol-water mixtures. In general, finding surfactants that are effective in alcohol-water mixtures is more challenging than finding ones that are effective in pure water. This is because the solvophobic effect that partitions surfactants from bulk solution to the interface becomes weaker as ethanol concentration increases. We use experiments and molecular dynamics to observe the effects of increasing surfactant tail length or width...
November 28, 2016: Journal of Chemical Physics
Tian Xia, Yaping Qin, Yajiang Huang, Ting Huang, Jianhui Xu, Youbing Li
The morphology evolution mechanism of polystyrene (PS)/poly (vinyl methyl ether) (PVME) blend thin films with different PS molecular weights (Mw) was studied. It was found that the morphology evolution was closely related to the molecular weight asymmetry between PS and PVME. In the film where Mw(PS) ≈ Mw(PVME), dewetting happened at the interface between the bottom layer and substrate after SD phase separation. While in the film where Mw(PS) > Mw(PVME), dewetting happened at the interface between the middle PS/PVME blend layer and bottom PVME layer near the substrate prior to phase separation...
November 28, 2016: Journal of Chemical Physics
Cheng Lian, Shuangliang Zhao, Honglai Liu, Jianzhong Wu
Understanding the charging kinetics of electric double layers is of fundamental importance for the design and development of novel electrochemical devices such as supercapacitors and field-effect transistors. In this work, we study the dynamic behavior of room-temperature ionic liquids using a classical time-dependent density functional theory that accounts for the molecular excluded volume effects, the electrostatic correlations, and the dispersion forces. While the conventional models predict a monotonic increase of the surface charge with time upon application of an electrode voltage, our results show that dispersion between ions results in a non-monotonic increase of the surface charge with the duration of charging...
November 28, 2016: Journal of Chemical Physics
Yun-An Yan
Over decades, the theoretical study of the quantum dissipative dynamics was mainly based on the linear dissipation model. The study of the nonlinear dissipative dynamics in condensed phases, where there exist an infinite number of bath modes, is extremely difficult even if not impossible. This work put forward a stochastic scheme for the simulation of the nonlinear dissipative dynamics. In the linear response regime, the second-order cumulant expansion becomes exact to reproduce the effect of the bath on the evolution of the reduced system...
November 28, 2016: Journal of Chemical Physics
P Garbacz, A D Buckingham
It is predicted that, for two spin-1/2 nuclei coupled by indirect spin-spin coupling in a chiral molecule, chirality-sensitive induced electric polarization can be observed at the frequencies equal to the sum and difference between the spin resonance frequencies. Also, an electric field oscillating at the difference frequency can induce spin coherences which allow the direct discrimination between enantiomers by nuclear magnetic resonance. The dominant contribution to the magnitude of these expected chiral effects is proportional to the permanent electric dipole moment and to the antisymmetric part of the indirect spin-spin coupling tensor of the chiral molecule...
November 28, 2016: Journal of Chemical Physics
Aishani Ghosal, Binny J Cherayil
In an extension of earlier studies from this group on the application of the Jarzynski equality to the determination of the elastic properties of a finitely extensible Rouse model of polymers under flow [A. Ghosal and B. J. Cherayil, J. Chem. Phys. 144, 214902 (2016)], we derive several new theoretical results in this paper on the nature of the distribution function P(w) that governs the long-time limit t>1 of the fluctuations in the work w performed by the polymer during flow-induced stretching. In particular, we show that an expression for the average of the nth power of the work, ⟨w(n)(t)⟩, can be obtained in closed form in this limit, making it possible to exactly calculate three important statistical measures of P(w): the mean μ, the skewness γ1, and the kurtosis γ2 (apart from the variance σ(2))...
November 28, 2016: Journal of Chemical Physics
Amir Saadat, Bamin Khomami
A bead-spring model for semi-flexible macromolecules is developed to overcome the deficiencies of the current coarse-grained bead-spring models. Specifically, model improvements are achieved through incorporation of a bending potential. The new model is designed to accurately describe the correlation along the backbone of the chain, segmental length, and force-extension behavior of the macromolecule even at the limit of 1 Kuhn step per spring. The relaxation time of different Rouse modes is used to demonstrate the capabilities of the new model in predicting chain dynamics...
November 28, 2016: Journal of Chemical Physics
Daniel Leicht, Matin Kaufmann, Raffael Schwan, Jan Schäfer, Gerhard Schwaab, Martina Havenith
The IR spectrum of benzyl radical:water clusters was recorded. Benzyl radicals were produced by vacuum flash pyrolysis and trapped in superfluid helium nanodroplets. The infrared spectrum of benzyl radical water aggregates in the range 2585-2820 cm(-1) was recorded by subsequent addition of deuterated water. A total of seven peaks are observed at 2766, 2750, 2656, 2638, 2633, 2598, and 2593 cm(-1). Based on pressure dependent measurements and comparison to accompanying ab initio calculations, five of these bands are assigned to distinct O-D stretch vibrations of benzyl:water clusters with one and two water molecules...
November 28, 2016: Journal of Chemical Physics
Christoph E Sitta, Frank Smallenburg, Raphael Wittkowski, Hartmut Löwen
Combining analytic calculations, computer simulations, and classical density functional theory we determine the interfacial tension of orientable two-dimensional hard rectangles near a curved hard wall. Both a circular cavity holding the particles and a hard circular obstacle surrounded by particles are considered. We focus on moderate bulk densities (corresponding to area fractions up to 50%) where the bulk phase is isotropic and vary the aspect ratio of the rectangles and the curvature of the wall. The Tolman length, which gives the leading curvature correction of the interfacial tension, is found to change sign at a finite density, which can be tuned via the aspect ratio of the rectangles...
November 28, 2016: Journal of Chemical Physics
Ryan C Fortenberry
The HNNS radical has been promoted recently as a viable intermediate in the interstellar creation of the spectroscopically elusive nitrogen molecule. Any confirmation of this pathway or utilizing HNNS as a tracer of N2 depends upon the ability to observe the radical intermediate whether in the laboratory or in the interstellar medium. Established and accurate quantum chemical procedures are employed here to produce spectroscopic constants, fundamental vibrational frequencies, and intensities that can be utilized for any possible detection of HNNS...
November 28, 2016: Journal of Chemical Physics
J Zou, C Wu, W D Robertson, L V Zhigilei, R J D Miller
Molecular dynamics simulations were performed to characterize the ablation process induced by a picosecond infrared laser (PIRL) operating in the regime of desorption by impulsive vibrational excitation (DIVE) of a model peptide (lysozyme)/counter-ion system in aqueous solution. The simulations were performed for ablation under typical experimental conditions found within a time-of-flight mass spectrometer (TOF-MS), that is in vacuum with an applied electric field (E = ± 10(7) V/m), for up to 2 ns post-ablation and compared to the standard PIRL-DIVE ablation condition (E = 0 V/m)...
November 28, 2016: Journal of Chemical Physics
Alicia Rae Welden, Alexander A Rusakov, Dominika Zgid
Including finite-temperature effects from the electronic degrees of freedom in electronic structure calculations of semiconductors and metals is desired; however, in practice it remains exceedingly difficult when using zero-temperature methods, since these methods require an explicit evaluation of multiple excited states in order to account for any finite-temperature effects. Using a Matsubara Green's function formalism remains a viable alternative, since in this formalism it is easier to include thermal effects and to connect the dynamic quantities such as the self-energy with static thermodynamic quantities such as the Helmholtz energy, entropy, and internal energy...
November 28, 2016: Journal of Chemical Physics
Nikolay D Kondratyuk, Genri E Norman, Vladimir V Stegailov
Diffusion is one of the key subjects of molecular modeling and simulation studies. However, there is an unresolved lack of consistency between Einstein-Smoluchowski (E-S) and Green-Kubo (G-K) methods for diffusion coefficient calculations in systems of complex molecules. In this paper, we analyze this problem for the case of liquid n-triacontane. The non-conventional long-time tails of the velocity autocorrelation function (VACF) are found for this system. Temperature dependence of the VACF tail decay exponent is defined...
November 28, 2016: Journal of Chemical Physics
Matthew J Turnbull, Daniel Vaccarello, Yun Mui Yiu, Tsun-Kong Sham, Zhifeng Ding
Solar cell performance is most affected by the quality of the light absorber layer. For thin-film devices, this becomes a two-fold problem of maintaining a low-cost design with well-ordered nanocrystal (NC) structure. The use of Cu2ZnSnS4 (CZTS) NCs as the light absorber films forms an ideal low-cost design, but the quaternary structure makes it difficult to maintain a well-ordered layer without the use of high-temperature treatments. There is little understanding of how CZTS NC structures affect the photoconversion efficiency, the charge-carriers, and therefore the performance of the device manufactured from it...
November 28, 2016: Journal of Chemical Physics
Y Zhang, R Ashcraft, M I Mendelev, C Z Wang, K F Kelton
The state-of-the-art experimental and atomistic simulation techniques were utilized to study the structure of the liquid and amorphous Ni62Nb38 alloy. First, the ab initio molecular dynamics (AIMD) simulation was performed at rather high temperature where the time limitations of the AIMD do not prevent to reach the equilibrium liquid structure. A semi-empirical potential of the Finnis-Sinclair (FS) type was developed to almost exactly reproduce the AIMD partial pair correlation functions (PPCFs) in a classical molecular dynamics simulation...
November 28, 2016: Journal of Chemical Physics
Hans-Joachim Werner
The accuracy of multipole approximations for distant pair energies in local second-order Møller-Plesset perturbation theory (LMP2) as introduced by Hetzer et al. [Chem. Phys. Lett. 290, 143 (1998)] is investigated for three chemical reactions involving molecules with up to 92 atoms. Various iterative and non-iterative approaches are compared, using different energy thresholds for distant pair selection. It is demonstrated that the simple non-iterative dipole-dipole approximation, which has been used in several recent pair natural orbitals (PNO)-LMP2 and PNO-LCCSD (local coupled-cluster with singles and doubles) methods, may underestimate the distant pair energies by up to 50% and can lead to significant errors in relative energies, unless very tight thresholds are used...
November 28, 2016: Journal of Chemical Physics
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