Microwave spectroscopic and theoretical investigations of the strongly hydrogen bonded hexafluoroisopropanol...water complex

This paper reports microwave spectroscopic and theoretical investigations on the interaction of water with hexafluoroisopropanol (HFIP). The HFIP monomer can exist in two conformations, antiperiplanar (AP) and synclinical (SC). The former is about 5 kJ mol(-1) more stable than the latter. Theoretical calculations predicted three potential minima for the complex, two having AP and one having SC conformations. Though, the binding energy for the HFIP(SC)...H2O turned out to be larger than that for the other two conformers having HFIP in the AP form, the global minimum for the complex in the potential energy hypersurface had HFIP in the AP form. Experimental rotational constants for four isotopologues measured using a pulsed nozzle Fourier transform microwave spectrometer, correspond to the global minimum in the potential energy hypersurface. The structural parameters and the internal dynamics of the complex could be determined from the rotational spectra of the four isotopologues. The global minimum has the HFIP(AP) as a hydrogen bond donor forming a strong hydrogen bond with H2O. To characterize the strength of the bonding and to probe the other interactions within the complex, atoms in molecules, non-covalent interaction index and natural bond orbital theoretical analyses have been performed.

Towards an exact factorization of the molecular wave function

An exact single-product factorisation of the molecular wave function for the timedependent Schrodinger equation is investigated by using an ansatz involving a phasefactor. By using the Frenkel variational method, we obtain the Schrodinger equations for the electronic and nuclear wave functions. The concept of a potential energy surface (PES) is retained by introducing a modified Hamiltonian as suggested earlier by Cederbaum. The parameter in the phase factor is chosen such that the equations of motion retain the physically appealing Born- Oppenheimer-like form, and is therefore unique.

Triplet excited electronic state switching induced by hydrogen bonding: A transient absorption spectroscopy and time-dependent DFT study

The solvent plays a decisive role in the photochemistry and photophysics of aromatic ketones. Xanthone (XT) is one such aromatic ketone and its triplet-triplet (T-T) absorption spectra show intriguing solvatochromic behavior. Also, the reactivity of XT towards H-atom abstraction shows an unprecedented decrease in protic solvents relative to aprotic solvents. Therefore, a comprehensive solvatochromic analysis of the triplet-triplet absorption spectra of XT was carried out in conjunction with time dependent density functional theory using the ad hoc explicit solvent model approach. A detailed solvatochromic analysis of the T-T absorption bands of XT suggests that the hydrogen bonding interactions are different in the corresponding triplet excited states. Furthermore, the contributions of non-specific and hydrogen bonding interactions towards differential solvation of the triplet states in protic solvents were found to be of equal magnitude. The frontier molecular orbital and electron density difference analysis of the T-1 and T-2 states of XT indicates that the charge redistribution in these states leads to intermolecular hydrogen bond strengthening and weakening, respectively, relative to the S-0 state. This is further supported by the vertical excitation energy calculations of the XT-methanol supra-molecular complex. The intermolecular hydrogen bonding potential energy curves obtained for this complex in the S-0, T-1, and T-2 states support the model. In summary, we propose that the different hydrogen bonding mechanisms exhibited by the two lowest triplet excited states of XT result in a decreasing role of the n pi* triplet state, and are thus responsible for its reduced reactivity towards H-atom abstraction in protic solvents. (C) 2016 AIP Publishing LLC.

Duality and energy averaging for e+e- annihilation in potential models

Analytical expressions for the corrections to duality are obtained for nonsingular potentials, and are found to be small numerically. An alternative consistent way of energy smoothing, developed by Strutinsky, is elucidated. This may be of use even when potential models are not valid.

Metallo crown porphyrins as ionophores-metal dependent uncoupling of mitochondrial energy potential

Porphyrins appended with crown ether moieties function as efficient uncouplesrs of oxidative phorphorylation in rat liver mitochondria. Permeation of these highly organized porphyrins decrease the respiratory coefficient index (RCI) values. Lowering of the RCI values parallels the number of K+ chelating crown ether groups attached to the porphyrins. The inhibitory effect upon the oxidative phorphorylation reaction depends on the nature of divalent metal ions, VO, Co, Cu and Zn in the porphyrin cavity and related to their relative tendency to complex intracellular K+ ions.

Adsorption of carbon monoxide on the surfaces of polycrystalline transition metals and alloys: electron energy loss and ultraviolet photoelectron spectral studies1

Adsorption of CO has been investigated on the surfaces of polycrystalline transition metals as well as alloys by employing electron energy loss spectroscopy (eels) and ultraviolet photoelectron spectroscopy (ups). CO adsorbs on polycrystalline transition metal surfaces with a multiplicity of sites, each being associated with a characteristic CO stretching frequency; the relative intensities vary with temperature as well as coverage. Whilst at low temperatures (80- 120 K), low coordination sites are stabilized, the higher coordination sites are stabilized at higher temperatures (270-300 K). Adsorption on surfaces of polycrystalline alloys gives characteristic stretching frequencies due to the constituent metal sites. Alloying, however, causes a shift in the stretching frequencies, indicating the effect of the band structure on the nature of adsorption. The up spectra provide confirmatory evidence for the existence of separate metal sites in the alloys as well as for the high-temperature and low-temperature phases of adsorbed CO.

Metallo crown porphyrins as ionophores-metal dependent uncoupling of mitochondrial energy potential

Porphyrins appended with crown ether moieties function as efficient uncouplesrs of oxidative phorphorylation in rat liver mitochondria. Permeation of these highly organized porphyrins decrease the respiratory coefficient index (RCI) values. Lowering of the RCI values parallels the number of K+ chelating crown ether groups attached to the porphyrins. The inhibitory effect upon the oxidative phorphorylation reaction depends on the nature of divalent metal ions, VO, Co, Cu and Zn in the porphyrin cavity and related to their relative tendency to complex intracellular K+ ions.

Potential functions for hydrogen bond interactions - IV. Minimum Energy Conformation of the α-Helical Structure of PoIy-L-Alanine

Making use of the empirical potential functions for peptide NH .. O bonds, developed in this laboratory, the relative stabilities of the rightand left-handed α-helical structures of poly-L-alanine have been investigated, by calculating their conformational energies (V). The value of Vmin of the right-handed helix (αP) is about - 10.4 kcal/mole, and that of the left-handed helix (αM) is about - 9.6 kcal/mole, showing that the former is lower in energy by 0.8 kcal/mole. The helical parameters of the stable conformation of αP are n ∼ 3.6 and h ∼ 1.5 Å. The hydrogen bond of length 2.85 Å and nonlinearity of about 10° adds about 4.0 kcal/ mole to the stabilising energy of the helix in the minimum enregy region. The energy minimum is not sharply defined, but occurs over a long valley, suggesting that a distribution of conformations (φ{symbol}, ψ) of nearly the same energy may occur for the individual residues in a helix. The experimental data of a-helical fibres of poly-L-alanine are in good agreement with the theoretical results for αP. In the case of proteins, the mean values of (φ{symbol}, ψ) for different helices are distributed, but they invariably occur within the contour for V = Vmin + 2 kcal/mole for αP.

Exact energy eigenvalues for an attractive Coulomb potential with zero-radius hard core

Following a peratization procedure, the exact energy eigenvalues for an attractive Coulomb potential, with a zero-radius hard core, are obtained as roots of a certain combination of di-gamma functions. The physical significance of this entirely new energy spectrum is discussed.

Surface modifications in single crystal surfaces of YBa2Cu3O7-delta upon high energy ion irradiation

Atomic force microscopy investigations on swift heavy ion (200 MeV An) irradiated surfaces of a high T-c single crystal YBa2Cu3O7-delta are presented. Results obtained revealed an ion-induced erosion/sputtering clearly confirming our earlier observation on grain boundary dominated thin films. Apart from sputtering, notable effects were seen with many defect structures like dikes/hillocks surrounded by craters, dikes, holes, pearl like structures and ripple formation of sub-micron undulations, all in one crystal. Results are discussed in the light of co-operative phenomena of material re-distribution mechanism related to mass transfer and crater formations.

Flat connections, geometric invariants and energy of harmonic functions on compact Riemann surfaces

A geometric invariant is associated to the space of fiat connections on a G-bundle over a compact Riemann surface and is related to the energy of harmonic functions.

Estimation of surface free energy of pyrites by contact angle measurements

The surface properties of coal-pyrite play a major role in determining its separation from coal in processes such as flotation. The solution pH is an important parameter in determining the surface properties of both coal and coal-pyrite such as surface free energy and zeta-potential. In the present investigation, the effect of pH on the surface free energy of pyrites from different sources was studied. The surface free energy of solids is made up of two components, i.e. the dispersive surface free energy and the acid-base interaction energy. Various methods have been used by previous researchers to evaluate these two components for different solids. In the present study, a new approach was developed and used to study the surface free energy of pyrite surfaces. Results indicate that the dispersion surface free energy of various pyrites is independent of pH while the acid-base interaction energy is strongly dependent on the pH. The acid-base interaction energy is different for each pyrite sample and also the change with pH varies with the type of pyrite. Coal-pyrite was found to be more hydrophobic than ore-pyrite which may be attributed to the presence of carbon in coal-pyrites. The acid-base interaction energy varied little with pH for coal pyrites than ore-pyrite. Comparison of acid-base interaction energy with zeta-potential measurements shows a good correlation between the minimum in acid-base interaction energy and the pHpzc.

WEPA: Wind energy potential assessment-spatial decision support system

Spatial Decision Support System (SDSS) assist in strategic decision-making activities considering spatial and temporal variables, which help in Regional planning. WEPA is a SDSS designed for assessment of wind potential spatially. A wind energy system transforms the kinetic energy of the wind into mechanical or electrical energy that can be harnessed for practical use. Wind energy can diversify the economies of rural communities, adding to the tax base and providing new types of income. Wind turbines can add a new source of property value in rural areas that have a hard time attracting new industry. Wind speed is extremely important parameter for assessing the amount of energy a wind turbine can convert to electricity: The energy content of the wind varies with the cube (the third power) of the average wind speed. Estimation of the wind power potential for a site is the most important requirement for selecting a site for the installation of a wind electric generator and evaluating projects in economic terms. It is based on data of the wind frequency distribution at the site, which are collected from a meteorological mast consisting of wind anemometer and a wind vane and spatial parameters (like area available for setting up wind farm, landscape, etc.). The wind resource is governed by the climatology of the region concerned and has large variability with reference to space (spatial expanse) and time (season) at any fixed location. Hence the need to conduct wind resource surveys and spatial analysis constitute vital components in programs for exploiting wind energy. SDSS for assessing wind potential of a region / location is designed with user friendly GUI’s (Graphic User Interface) using VB as front end with MS Access database (backend). Validation and pilot testing of WEPA SDSS has been done with the data collected for 45 locations in Karnataka based on primary data at selected locations and data collected from the meteorological observatories of the India Meteorological Department (IMD). Wind energy and its characteristics have been analysed for these locations to generate user-friendly reports and spatial maps. Energy Pattern Factor (EPF) and Power Densities are computed for sites with hourly wind data. With the knowledge of EPF and mean wind speed, mean power density is computed for the locations with only monthly data. Wind energy conversion systems would be most effective in these locations during May to August. The analyses show that coastal and dry arid zones in Karnataka have good wind potential, which if exploited would help local industries, coconut and areca plantations, and agriculture. Pre-monsoon availability of wind energy would help in irrigating these orchards, making wind energy a desirable alternative.

Solar energy potential assessment using GIS

Renewable energy resources are those having a cycling time less than 100 years and are renewed by the nature and their supply exceeds the rate of consumption. Renewable energy systems use resources that are constantly replaced in nature and are usually less polluting. In order to tap the potential of renewable energy sources, there is a need to assess the availability of resources spatially as well as temporally. Geographic Information Systems (GIS) along with Remote Sensing (RS) helps in mapping on spatial and temporal scales of the resources and demand. The spatial database of resource availability and the demand would help in the regional energy planning. This paper discusses the application of geographical information system (GIS) to map the solar potential in Karnataka state, India. Regions suitable for tapping solar energy are mapped on the basis of global solar radiation data, and this analysis provides a picture of the potential. The study identifies that Coastal parts of Karnataka with the higher global solar radiation is ideally suited for harvesting solar energy. The potential analysis reveals that, maximum global solar radiation is in districts such as Uttara Kannada and Dakshina Kannada. Global solar radiation in Uttara Kannada during summer, monsoon and winter are 6.31, 4.40 and 5.48 kWh/sq.m, respectively. Similarly, Dakshina Kannada has 6.16, 3.89 and 5.21 kWh/sq.m during summer, monsoon and winter.