Jochen Schmidt

Isobaric−Isothermal Molecular Dynamics Simulations Utilizing Density Functional Theory: An Assessment of the Structure and Density of Water at Near-Ambient Conditions

We present herein a comprehensive density functional theory study toward assessing the accuracy of two popular gradient-corrected exchange correlation functionals on the structure and density of liquid water at near ambient conditions in the isobaric-isothermal ensemble. Our results indicate that both PBE and BLYP functionals under predict the density and over structure the liquid. Adding the dispersion correction due to Grimme (1, 2) improves the predicted densities for both BLYP and PBE in a significant manner. Moreover, the addition of the dispersion correction for BLYP yields an oxygen-oxygen radial distribution function in excellent agreement with experiment. Thus, we conclude that one can obtain a very satisfactory model for water using BLYP and a correction for dispersion.

Ionic Charge Reduction and Atomic Partial Charges from First-Principles Calculations of 1,3-Dimethylimidazolium Chloride

We present a detailed calculation of partial charges for the 1,3-dimethylimidazolium chloride ionic liquid. We first analyze MP2 electronic structure calculations and DFT results on isolated ion pairs with various methods of assigning partial charges to the atomic centers. In a second run we analyze the trajectory of a 25 ps long Car-Parrinello MD run of 30 ion pairs under bulk conditions using a charge fitting procedure due to Blöchl. Both, the single ion pair and the bulk system, provide us with a similar total ionic charge considerably less than unity. Especially the liquid state DFT results give convincing evidence for a reduced ionic charge on the ions. The similarity of both results suggest that the delocalization of the Cl charge is due only to local interactions. The relevance of our results is 2-fold; on the one hand they shed light on the basic property of the liquid and its reduced ionic character, and on the other hand, the ab initio derived partial charges provide a fundamental theoretical basis for the recent attempts to use the total ionic charge as an adjustable parameter. Furthermore, all our partial charges are subject to large fluctuations, hinting to the importance of polarization effects.

A comparative study of two classical force fields on statics and dynamics of [EMIM][BF4] investigated via molecular dynamics simulations

The influences of two different commonly employed force fields on statical and dynamical properties of ionic liquids are investigated for [EMIM][BF(4)]. The force fields compared in this work are the one of Canongia Lopes and Padua [J. Phys. Chem. B 110, 19586 (2006)] and that of Liu et al. [J. Phys. Chem. B 108, 12978 (2004)]. Differences in the strengths of hydrogen bonds are found, which are also reflected in the static ion distributions around the cation. Moreover, due to the stronger hydrogen bonding in the force field of Liu et al., the diffusive motions of cations and anions and the rotational behavior of the cations are slower compared with those obtained with the force field of Canongia Lopes and Padua. Both force fields underestimate the zero-field electrical conductivity, while the experimental dielectric constant can be reproduced within the expected statistical error boundaries.

Study of 1,3-dimethylimidazolium chloride with electronic structure methods and force field approaches.

The 1,3-dimethyl imidazolium chloride [MMIM]Cl is an example of ionic liquid and frequently studied in literature. In this article [MMIM]Cl is studied using an ab initio method [second order Moller-Plesset perturbation theory (MP2), density functional theory (DFT)] and classical force field approach with the aim of looking at some properties on different scales. Selected properties are studied with the different methods and compared to each other. The comparison between the results obtained with MP2 and the DFT approach allows us to comment on the validity of this latter and thus on its employment in larger systems. On the other hand, the comparison between the DFT results and those of the classical approach allows us to test the reproducibility of electrostatic properties by this latter approach. As the results show the used DFT setup is rather satisfactory, while the classical force fields are describing the electrostatic properties in an insufficient way. A revision (improvement) of the classical force fields is at this stage necessary in order to capture the electrostatic properties in a proper way.

TPA induces apoptosis in MPC−11 mouse plasmacytoma cells grown in serum−free medium

Apoptotic-like events could be rapidly induced by the phorbol ester 12-O-tetradecanoylphorbol-13-acetate (TPA) in cells of the mouse plasmacytoma cell line MPC-11 grown in serum-free medium. Indicators for apoptosis were morphological changes visualized by light and electron microscopy, such as chromatin condensation and the formation of cellular buds and fragments, as well as biochemical indices like the appearance of the so-called DNA ladder. Additionally, in these cells which are usually devoid of significant amounts of cytoplasmic intermediate filament (cIF) proteins, synthesis and accumulation of the cIF protein vimentin was rapidly induced by TPA treatment and almost all cells became vimentin-positive. Later on, substantial amounts of vimentin and lamin B degradation products appeared, and an increasing fraction of cells displayed low or even undetectable quantities of intact vimentin. This subpopulation was characterized via microscopy to be in the late stages of apoptosis. We suggest that in MPC-11 cells undergoing apoptosis in response to TPA treatment vimentin as well as lamin B are degraded, leading to a rearrangement and eventual loss of their respective filament networks.