Molecular dynamics and simulations study on the vibrational and electronic solvatochromism of benzophenone

Solvent plays a key role in diverse physico-chemical and biological processes. Therefore, understanding solute-solvent interactions at the molecular level of detail is of utmost importance. A comprehensive solvatochromic analysis of benzophenone (Bzp) was carried out in various solvents using Raman and electronic spectroscopy, in conjunction with Density Functional Theory (DFT) calculations of supramolecular solute-solvent clusters generated using classical Molecular Dynamics Simulations (c-MDSs). The >C=O stretching frequency undergoes a bathochromic shift with solvent polarity. Interestingly, in protic solvents this peak appears as a doublet: c-MDS and ad hoc explicit solvent ab initio calculations suggest that the lower and higher frequency peaks are associated with the hydrogen bonded and dangling carbonyl group of Bzp, respectively. Additionally, the dangling carbonyl in methanol (MeOH) solvent is 4 cm(-1) blue-shifted relative to acetonitrile solvent, despite their similar dipolarity/polarizability. This suggests that the cybotactic region of the dangling carbonyl group in MeOH is very different from its bulk solvent structure. Therefore, we propose that this blue-shift of the dangling carbonyl originates in the hydrophobic solvation shell around it resulting from extended hydrogen bonding network of the protic solvents. Furthermore, the 1(1)n pi* (band I) and 1(1)pi pi* (band II) electronic transitions show a hypsochromic and bathochromic shift, respectively. In particular, these shifts in protic solvents are due to differences in their excited state-hydrogen bonding mechanisms. Additionally, a linear relationship is obtained for band I and the >C=O stretching frequency (cm(-1)), which suggests that the different excitation wavelengths in band I correspond to different solvation states. Therefore, we hypothesize that the variation in excitation wavelengths in band I could arise from different solvation states leading to varying solvation dynamics. This will have implications for ultrafast processes associated with electron-transfer, charge transfer, and also the photophysical aspects of excited states. (C) 2016 AIP Publishing LLC.

Space-Vector-Based Hybrid PWM Technique to Reduce Peak-to-Peak Torque Ripple in Induction Motor Drives

Constant-volts-per-hertz induction motor drives and vector-controlled induction motor drives utilize pulsewidth modulation (PWM) to control the voltage applied on the motor. The method of PWM influences the pulsations in the torque developed by the motor. A space-vector-based approach to PWM facilitates special switching sequences involving the division of active state time. This paper proposes a space-vector-based hybrid PWM technique, which is a combination of the conventional and special switching sequences. The proposed hybrid PWM technique results in a lower peak-to-peak torque ripple than conventional space vector PWM(CSVPWM) at high speeds of an induction motor drive. Furthermore, the magnitude of the dominant torque harmonic due to the proposed hybrid PWM is significantly lower than that due to CSVPWM at high speeds of the drive. Experimental results from a 3.75-kW sensorless vector-controlled induction motor drive under various load conditions are presented to support analytical and simulation results.

Effect of particle size of sand and surface asperities of reinforcement on their interface shear behaviour

This paper investigates the effect of particle size of sand and the surface asperities of reinforcing material on their interlocking mechanism and its influence on the interfacial shear strength under direct sliding condition. Three sands of different sizes with similar morphological characteristics and four different types of reinforcing materials with different surface features were used in this study. Interface direct shear tests on these materials were performed in a specially developed symmetric loading interface direct shear test setup. Morphological characteristics of sand particles were determined from digital image analysis and the surface roughness of the reinforcing materials was measured using an analytical expression developed for this purpose. Interface direct shear tests at three different normal stresses were carried out by shearing the sand on the reinforcing material fixed to a smooth surface. Test results revealed that the peak interfacial friction and dilation angles are hugely dependent upon the interlocking between the sand particles and the asperities of reinforcing material, which in turn depends on the relative size of sand particles and asperities. Asperity ratio (AS/D-50) of interlocking materials, which is defined as the ratio of asperity spacing of the reinforcing material and the mean particle size of sand was found to govern the interfacial shear strength with highest interfacial strength measured when the asperity ratio was equal to one, which represents the closest fitting of sand particles into the asperities. It was also understood that the surface roughness of the reinforcing material influences the shear strength to an extent, the influence being more pronounced in coarser particles. Shear bands in the interface shear tests were analysed through image segmentation technique and it was observed that the ratio of shear band thickness (t) to the median particle size (D-50) was maximum when the AS/D-50 was equal to one. (C) 2015 Elsevier Ltd. All rights reserved.

Intensity Distribution Design for Laser-Induced Thermal Loading Based on Numerical Simulation

To accomplish laser-induced thermal loading simulation tests for pistons,the Gaussian beam was modulated into multi-circular beam with specific intensity distribution.A reverse method was proposed to design the intensity distribution for the laser-induced thermal loading based on finite element(FE) analysis.Firstly,the FE model is improved by alternating parameters of boundary conditions and thermal-physical properties of piston material in a reasonable range,therefore it can simulate the experimental resul...

Comparative studies of AOT and NaDEHP by fluorescence technique and z-potential (ζ) measurements

The aggregation behaviors of two surfactants with the same hydrophobic tail, sodium bis(2-ethylhexyl)sulfosuccinate (AOT) and sodium bis(2-ethylhexyl)phosphate (NaDEHP), have been investigated by the fluorescence technique and z-potential (ζ) measurements. Five fine peaks of the pyrene molecule fluorescence spectroscopy appear in the surfactant solution, and the micropolarity at which pyrene locates is monitored from the intensity ratio of the first (I1) and the third peak (I3). A wide peak around 475 nm, the emission spectra of the excimer of pyrene molecules, is observed in the NaDEHP solution, while this is not found for the AOT system. The value of I1/I3 decreases in a more limited concentration range for the AOT system than for NaDEHP, indicating that small aggregates can be more easily formed by NaDEHP molecules. The z-potential results for the aggregates formed by the two surfactants show that the interaction between AOT and PVP is stronger than that between NaDEHP and PVP.

Mechanism on Progressive Failure of a Faulted Rock Slope Due to Slip-Weakening

Slip-weakening is one of the characteristics of geological materials under certain loadings. Non-uniform rock structure may exist in the vicinity of the slip surface for a rock slope. Some portion of the slip surface may be penetrated but the other not. For the latter case, the crack or the fault surface will undergo shear deformation before it becomes a successive surface under a certain loading. As the slipped portion advances,slip-weakening occurs over a distance behind the crack tip. In the weakening zone, the shear strength will decrease from its peak value to residual friction level. The stress will redistribute along the surface of crack and in the weakening zone. Thus the changed local stress concentration leads the crack to extend and the ratio of penetration of the slip surface to increase. From the view of large-scale for the whole slip surface, the shear strength will decrease due to the damage of interior rock structure, and the faulted rock behaves as a softening material. Such a kind of mechanism performs in a large number of practical landslides in the zones experienced strong earthquakes. It should be noted that the mechanism mentioned above is different from that of the breakage of structural clay,in which the geological material is regarded as a medium containing structural lumps and structural bands. In this paper, the softening behavior of a faulted rock should be regarded as a comprehensive result of the whole complicated process including slip-weakening, redistribution of stress, extension of crack tip, and the penetration of the slip surface. This process is accompanied by progressive failure and abrupt structural damage. The size of slip-weakening zone is related to the undergoing strain. Once the relative slide is initiated (local or integrated), the effect of slip-weakening will behave in a certain length behind the crack tip until the formation of the whole slip surface.