Two-Phase Thermodynamic Model for Efficient and Accurate Absolute Entropy of Water from Molecular Dynamics Simulations

Presented here is the two-phase thermodynamic (2PT) model for the calculation of energy and entropy of molecular fluids from the trajectory of molecular dynamics (MD) simulations. In this method, the density of state (DoS) functions (including the normal modes of translation, rotation, and intramolecular vibration motions) are determined from the Fourier transform of the corresponding velocity autocorrelation functions. A fluidicity parameter (f), extracted from the thermodynamic state of the system derived from the same MD, is used to partition the translation and rotation modes into a diffusive, gas-like component (with 3Nf degrees of freedom) and a nondiffusive, solid-like component. The thermodynamic properties, including the absolute value of entropy, are then obtained by applying quantum statistics to the solid component and applying hard sphere/rigid rotor thermodynamics to the gas component. The 2PT method produces exact thermodynamic properties of the system in two limiting states: the nondiffusive solid state (where the fluidicity is zero) and the ideal gas state (where the fluidicity becomes unity). We examine the 2PT entropy for various water models (F3C, SPC, SPC/E, TIP3P, and TIP4P-Ew) at ambient conditions and find good agreement with literature results obtained based on other simulation techniques. We also validate the entropy of water in the liquid and vapor phases along the vapor-liquid equilibrium curve from the triple point to the critical point. We show that this method produces converged liquid phase entropy in tens of picoseconds, making it an efficient means for extracting thermodynamic properties from MD simulations.

Contribution of different physical forces to the disjoining pressure of a thin water film being pressed by an oil droplet

With an objective to understand the nature of forces which contribute to the disjoining pressure of a thin water film on a steel substrate being pressed by an oil droplet, two independent sets of experiments were done. (i) A spherical silica probe approaches the three substrates; mica, PTFE and steel, in a 10 mM electrolyte solution at two different pHs (3 and 10). (ii) The silica probe with and without a smeared oil film approaches the same three substrates in water (pH = 6). The surface potential of the oil film/water was measured using a dynamic light scattering experiment. Assuming the capacity of a substrate for ion exchange the total interaction force for each experiment was estimated to include the Derjaguin-Landau-Verwey-Overbeek (DLVO) force, hydration repulsion, hydrophobic attraction and oil-capillary attraction. The best fit of these estimates to the force-displacement characteristics obtained from the two sets of experiment gives the appropriate surface potentials of the substrates. The procedure allows an assessment of the relevance of a specific physical interaction to an experimental configuration. Two of the principal observations of this work are: (i) The presence of a surface at constant charge, as in the presence of an oil film on the probe, significantly enhances the counterion density over what is achieved when both the surfaces allow ion exchange. This raises the corresponding repulsion barrier greatly. (ii) When the substrate surface is wettable by oil, oil-capillary attraction contributes substantially to the total interaction. If it is not wettable the oil film is deformed and squeezed out. (C) 2010 Elsevier Inc. All rights reserved.

Note: Dynamic point spread function for single and multiphoton fluorescence microscopy

We propose and demonstrate a dynamic point spread function (PSF) for single and multiphoton fluorescence microscopy. The goal is to generate a PSF whose shape and size can be maneuvered from highly localized to elongated one, thereby allowing shallow-to-depth excitation capability during active imaging. The PSF is obtained by utilizing specially designed spatial filter and dynamically altering the filter parameters. We predict potential applications in nanobioimaging and fluorescence microscopy.

Single-File Diffusion of Confined Water Inside SWNTs: An NMR Study

We report a nuclear magnetic resonance (NMR) study of confined water inside similar to 1.4 nm diameter single-walled carbon nanotubes (SWNTs). We show that the confined water does not freeze even up to 223 K. A pulse field gradient (PFG) NMR method is used to determine the mean squared displacement (MSD) of the water molecules inside the nanotubes at temperatures below 273 K, where the bulk water outside the nanotubes freezes and hence does not contribute to the proton NMR signal. We show that the mean squared displacement varies as the square root of time, predicted for single-file diffusion in a one-dimensional channel. We propose a qualitative understanding of our results based on available molecular dynamics simulations.

Single-File Diffusion of Water Inside Narrow Carbon Nanorings

We use atomistic molecular dynamics (MD) simulations to study the diffusion of water molecules confined inside narrow (6,6) carbon nanorings. The water molecules form two oppositely polarized chains. It is shown that the effective interaction between these two chains is repulsive in nature. The computed mean-squared displacement (MSD) clearly shows a scaling with time similar to t(1/2), which is consistent with single-file diffusion (SFD). The time up to which the water molecules undergo SFD is shown to be the lifetime of the water molecules inside these chains. Simulations of "uncharged" water molecules inside the nanoring show the formation of several water chains and yield SFD. These observations conclusively prove that the diffusion is Fickian when there is a single chain of water and SFD is observed only when two or more chains are present.

Five-kilowatt wood gasifier technology: Evolution and field experience

Various elements of an efficient and reliable 5k W wood gasifier system developed over the last ten years are described. The good performance obtained from the system is related to the careful design of its components and sub-systems. Results from extensive testing of gasifier prototypes at two national centres are discussed along with the experience gained in the field from their use at more than one hundred and fifty locations spread over five states in the country. Issues related to acceptance of the technology are also included. Improvements in design to extend the life, to reduce the cost, and to reduce the number of components are also discussed. A few variants of the design to meet the specific requirements of water pumping, power generation and to exploit specific site characteristics are presented.

COMMON-Sense net:Improved water management for resource-poor farmers via sensor networks

We describe the on-going design and implementation of a sensor network for agricultural management targeted at resource-poor farmers in India. Our focus on semi-arid regions led us to concentrate on water-related issues. Throughout 2004, we carried out a survey on the information needs of the population living in a cluster of villages in our study area. The results highlighted the potential that environment-related information has for the improvement of farming strategies in the face of highly variable conditions, in particular for risk management strategies (choice of crop varieties, sowing and harvest periods, prevention of pests and diseases, efficient use of irrigation water etc.). This leads us to advocate an original use of Information and Communication Technologies (ICT). We believe our demand-driven approach for the design of appropriate ICT tools that are targeted at the resource-poor to be relatively new. In order to go beyond a pure technocratic approach, we adopted an iterative, participatory methodology.

Interfacial microrheology as a tool to study viscoelastic transitions in nanoconfined soft matter

We present a method to perform in situ microrheological measurements on monolayers of soft materials undergoing viscoelastic transitions under compression. Using the combination of a Langmuir trough mounted on the inverted microscope stage of a laser scanning confocal microscope we track the motion of individual fluorescent quantum dots partly dispersed in monolayers spread at the air-water interface. From the calculated mean square displacement of the probe particles and extending a well established scheme of the generalized Stokes-Einstein relation in bulk to the interface we arrive at the viscoelastic modulus for the respective monolayers as a function of surface density. Measurements on monolayers of glassy as well as nonglassy polymers and a standard fatty acid clearly show sensitivity of our technique to subtle variations, in the viscoelastic properties of the highly confined materials under compression. Evidence for possible spatial variations of such viscoelastic properties at a given surface density for the fatty acid monolayer is also provided.

Effectiveness of a Differential Temperature Controller on a Solar Water Heating System: An Experimental Study

A differential temperature controller is incorporated in a solar water heating system to study the influence of its set points on system performance. The effectiveness of the controller set points DeltaT ON and DeltaT OFF on the pump cycling and energy collection has been studied experimentally and the results are presented in this paper.

Hills, dams and forests. Some field observations from the Western Ghats

Man’s attempts to intensify the use of natural resources can often result in the exhaustion of the resource or deterioration of other interacting resources. The single-minded pursuit of the development of the water resources of the rivers of the Western Ghats shows many examples of this view, particularly in the unnecessary destruction of the dwindling forest resources. This destruction may be caused by (i) problems o f rehabilitation, e.g. the Ramanagar settlement of the Kalinadi project (ii) the impact of labourers, e.g. the destruction of evergreen sholas on the Upper Nilgiri plateau (iii) the access to encroachers and poachers, e.g. Panshet and Kalinadi (iv) faulty planning, e.g. Linganamakki and Kalinadi. This destruction of forest cover has had a number of deleterious consequences in (i) worsening the shortages of forest resources, (ii) hastening the siltation of the reservoirs, (iii) ecological imbalances as in the rapid spread ofEupatorium in the Kalinadi project area and (iv) the decimation of biological diversity, as in the great reduction of evergreen forests in the Western Ghats, threatening the survival of lion-tailed macaque and the extinction of grass species,Hubbardia heptaneuron. It is stressed that the only sustainable and therefore true development is environmentally sound development. The interests of the weaker sections of the society often provide a good index of the soundness of the development from an environmental point of view. The planning of the development process with this perspective is a great scientific and technological challenge that must be taken up.

Sacrificial photolysis of water on Ti1−xSnxO2 ultrafine powders

Ultrafine powders of extra pure Ti1−xSnxO2, where o < x < 1, prepared by the hydrothermal method are pale yellow in color. They show photocatalytic activity after platinization, in the visible light (420–550 nm) for H2-production from aqueous solutions containing sacrificial donors such as hypophosphite. The spectral sensitization is shown to be due to peroxotitanium species in the rutile-type structure. Peroxide ion, O22−, arises from the dimerization of O−, the hole centres, produced during the disproportionative decomposition of residual hydroxyls: OH− = O− + H. Higher OH contents in TixSnxO2 is due to the amphoteric chemistry of oxocompounds of tin.