A thermal molecular migration in the solid-state - structures of isomeric 5-amino-4-(2,6-dichlorophenyl)-1-(2-nitrophenyl)-1h-1,2,3-triazole (yellow form i) and 4-(2,6-dichlorophenyl)-5-(2-nitroanilino)-2h-1,2,3-triazole (red form-ii), c14h9cl2n5o2

Yellow form (I): Mr= 350.09, monoclinic, P2Jn, Z--4, a=9.525(1), b=14.762(1), c= 11.268(1),/t, fl= 107.82 (1) o , V= 1508.3 A 3 , Din(flotation in aqueous KI)= 1.539 (2), D x= 1.541 (2) g cm -3, #(Cu Ka, 2 = 1.5418 A) = 40.58 cm -~, F(000) = 712, T= 293 K, R = 8.8% for 2054 significant refections. Red form (II): Mr= 350.09, triclinic, Pi, Z=2, a=9.796(2), b= 10.750 (2), c= 7.421 (1)A, a= 95.29 (2), fl= 0108-2701/84/111901-05501.50 70.18 (1), y = 92-.76 (2) °, V= 731.9 A 3, Din(flotation in KI) = 1.585 (3), D x = 1.588 (3) g cm -3, ~t(Cu Ka, 2 = 1.5418/~) = 40.58 cm -1, F(000) = 356, T=293 K, R = 5.8% for 1866 significant reflections. There are no unusual bond distances or angles. The triazole and two phenyl rings are planar. On the basis of packing considerations the possibility of intermolecular interactions playing a role in the reactivity of the starting material is ruled out.

Solvation and axial ligation properties of (2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato)zinc(II)

he solvation of (2,3,7,8,12,13,17,18-octabromo-5,10,15,20-tetraphenylporphyrinato)zinc(II)[Zn(obtpp)], in twelve different solvents results in large red shifts of the B and Q bands of the porphyrin accompanied by enhanced absorbance ratios of the Q bands. These observations are ascribed to the destabilisation of the highest occupied molecular orbital a2u of the porphyrin arising from a flow of charge from the axial ligand to the porphyrin ring through the zinc(II) ion. The binding constants of adducts of [Zn(obtpp)] with neutral bases have been found to be an order of magnitude greater than those observed for the corresponding adducts of (5,10,15,20-tetraphenylporphyrinato)-zinc and vary in the order piperidine > imidazole > pyridine > 3-methylpyridine > pyridine-3-carbaldehyde. The enhanced binding constants and large spectral shifts are interpreted in terms of the electrophilicity of [Zn(obtpp)] induced by the electron-withdrawing bromine substituents in the porphyrin core. The structure of [Zn(obtpp)(PrCN)2] has been determined; it reveals six-co-ordinated zinc(II) with two long Zn–N distance [2.51(4), 2.59(3)Å]. The porphyrin is non-planar and displays a saddle-shaped conformation.

B Physics: WHEPP-XI working group report

We present the report of the B physics working group of the Workshop on High Energy Physics Phenomenology (WHEPP-XI), held at the Physical Research Laboratory, Ahmedabad, in January 2010.

Absolute Entropy and Energy of Carbon Dioxide Using the Two-Phase Thermodynamic Model

The two-phase thermodynamic (2PT) model is used to determine the absolute entropy and energy of carbon dioxide over a wide range of conditions from molecular dynamics trajectories. The 2PT method determines the thermodynamic properties by applying the proper statistical mechanical partition function to the normal modes of a fluid. The vibrational density of state (DoS), obtained from the Fourier transform of the velocity autocorrelation function, converges quickly, allowing the free energy, entropy, and other thermodynamic properties to be determined from short 20-ps MD trajectories. The anharmonic effects in the vibrations are accounted for by the broadening of the normal modes into bands from sampling the velocities over the trajectory. The low frequency diffusive modes, which lead to finite DoS at zero frequency, are accounted for by considering the DoS as a superposition of gas-phase and solid-phase components (two phases). The analytical decomposition of the DoS allows for an evaluation of properties contributed by different types of molecular motions. We show that this 2PT analysis leads to accurate predictions of entropy and energy of CO2 over a wide range of conditions (from the triple point to the critical point of both the vapor and the liquid phases along the saturation line). This allows the equation of state of CO2 to be determined, which is limited only by the accuracy of the force field. We also validated that the 2PT entropy agrees with that determined from thermodynamic integration, but 2PT requires only a fraction of the time. A complication for CO2 is that its equilibrium configuration is linear, which would have only two rotational modes, but during the dynamics it is never exactly linear, so that there is a third mode from rotational about the axis. In this work, we show how to treat such linear molecules in the 2PT framework.

On breaks of the Indian monsoon

For over a century, the term break has been used for spells in which the rainfall over the Indian monsoon zone is interrupted. The phenomenon of 'break monsoon' is of great interest because long intense breaks are often associated with poor monsoon seasons. Such breaks have distinct circulation characteristics (heat trough type circulation) and have a large impact on rainfed agriculture. Although interruption of the monsoon rainfall is considered to be the most important feature of the break monsoon, traditionally breaks have been identified on the basis of the surface pressure and wind patterns over the Indian region. We have defined breaks (and active spells) on the basis of rainfall over the monsoon zone. The rainfall criteria are chosen so as to ensure a large overlap with the traditional breaks documented by Ramamurthy (1969) and De et al (1998). We have identified these rainbreaks for 1901-89. We have also identified active spells on the basis of rainfall over the Indian monsoon zone. We have shown that the all-India summer monsoon rainfall is significantly negatively correlated with the number of rainbreak days (correlation coefficient -0.56) and significantly positively correlated with the number of active days (correlation coefficient 0.47). Thus the interannual variation of the all-India summer monsoon rainfall is shown to be related to the number of days of rainbreaks and active spells identified here. There have been several studies of breaks (and also active spells in several cases) identified on the basis of different criteria over regions differing in spatial scales (e.g., Webster et al 1998; Krishnan et al 2000; Goswami and Mohan 2000; and Annamalai and Slingo 2001). We find that there is considerable overlap between the rainbreaks we have identified and breaks based on the traditional definition. There is some overlap with the breaks identified by Krishnan et al (2000) but little overlap with breaks identified by Webster et al (1998). Further, there are three or four active-break cycles in a season according to Webster et al (1998) which implies a time scale of about 40 days for which Goswami and Mohan (2000), and Annamalai and Slingo'(2001) have studied breaks and active minus break fluctuations. On the other hand, neither the traditional breaks (Ramamurthy 1969; and De et al 1998) nor the rainbreaks occur every year. This suggests that the 'breaks' in these studies axe weak spells of the intraseasonal variation of the monsoon, which occur every year. We have derived the OLR and circulation patterns associated with rainbreaks and active spells and compared them with the patterns associated with breaks/active minus break spells from these studies. Inspite of differences in the patterns over the Indian region, there is one feature which is seen in the OLR anomaly patterns of breaks identified on the basis of different criteria as well as the rainbreaks identified in this paper viz., a quadrapole over the Asia-west Pacific region arising from anomalies opposite (same) in sign to those over the Indian region occurring over the equatorial Indian Ocean and northern tropical (equatorial) parts of the west Pacific. Thus it appears that this quadrapole is a basic feature of weak spells of the intraseasonal,variation over the Asia-west Pacific region. Since the rainbreaks are intense weak spells, this basic feature is also seen in the composite patterns of these breaks. We find that rainbreaks (active spells) are also associated with negative (positive) anomalies over a part of the cast Pacific suggesting that the convection over the Indian region is linked to that over the east Pacific not only on the interannual scale (as evinced by the link between the Indian summer monsoon rainfall and ENSO) but on the intraseasonal scale as well.

Processes of 30-90 days sea surface temperature variability in the northern Indian Ocean during boreal summer

During summer, the northern Indian Ocean exhibits significant atmospheric intraseasonal variability associated with active and break phases of the monsoon in the 30-90 days band. In this paper, we investigate mechanisms of the Sea Surface Temperature (SST) signature of this atmospheric variability, using a combination of observational datasets and Ocean General Circulation Model sensitivity experiments. In addition to the previously-reported intraseasonal SST signature in the Bay of Bengal, observations show clear SST signals in the Arabian Sea related to the active/break cycle of the monsoon. As the atmospheric intraseasonal oscillation moves northward, SST variations appear first at the southern tip of India (day 0), then in the Somali upwelling region (day 10), northern Bay of Bengal (day 19) and finally in the Oman upwelling region (day 23). The Bay of Bengal and Oman signals are most clearly associated with the monsoon active/break index, whereas the relationship with signals near Somali upwelling and the southern tip of India is weaker. In agreement with previous studies, we find that heat flux variations drive most of the intraseasonal SST variability in the Bay of Bengal, both in our model (regression coefficient, 0.9, against similar to 0.25 for wind stress) and in observations (0.8 regression coefficient); similar to 60% of the heat flux variation is due do shortwave radiation and similar to 40% due to latent heat flux. On the other hand, both observations and model results indicate a prominent role of dynamical oceanic processes in the Arabian Sea. Wind-stress variations force about 70-100% of SST intraseasonal variations in the Arabian Sea, through modulation of oceanic processes (entrainment, mixing, Ekman pumping, lateral advection). Our similar to 100 km resolution model suggests that internal oceanic variability (i.e. eddies) contributes substantially to intraseasonal variability at small-scale in the Somali upwelling region, but does not contribute to large-scale intraseasonal SST variability due to its small spatial scale and random phase relation to the active-break monsoon cycle. The effect of oceanic eddies; however, remains to be explored at a higher spatial resolution.

Review of trend detection methods and their application to detect temperature changes in India

Present study performs the spatial and temporal trend analysis of annual, monthly and seasonal maximum and minimum temperatures (t(max), t(min)) in India. Recent trends in annual, monthly, winter, pre-monsoon, monsoon and post-monsoon extreme temperatures (t(max), t(min)) have been analyzed for three time slots viz. 1901-2003,1948-2003 and 1970-2003. For this purpose, time series of extreme temperatures of India as a whole and seven homogeneous regions, viz. Western Himalaya (WH), Northwest (NW), Northeast (NE), North Central (NC), East coast (EC), West coast (WC) and Interior Peninsula (IP) are considered. Rigorous trend detection analysis has been exercised using variety of non-parametric methods which consider the effect of serial correlation during analysis. During the last three decades minimum temperature trend is present in All India as well as in all temperature homogeneous regions of India either at annual or at any seasonal level (winter, pre-monsoon, monsoon, post-monsoon). Results agree with the earlier observation that the trend in minimum temperature is significant in the last three decades over India (Kothawale et al., 2010). Sequential MK test reveals that most of the trend both in maximum and minimum temperature began after 1970 either in annual or seasonal levels. (C) 2012 Elsevier B.V. All rights reserved.

Structure, dynamics and thermodynamics of single-file water under confinement: effects of polarizability of water molecules

Various structural, dynamic and thermodynamic properties of water molecules confined in single-wall carbon nanotubes (CNTs) are investigated using both polarizable and non-polarizable water models. The inclusion of polarizability quantitatively affects the nature of hydrogen bonding, which governs many properties of confined water molecules. Polarizable water leads to tighter hydrogen bonding and makes the distance between neighboring water molecules shorter than that for non-polarizable water. Stronger hydrogen bonding also decreases the rotational entropy and makes the diffusion constant smaller than in TIP3P and TIP3PM water models. The reorientational dynamics of the water molecules is governed by a jump mechanism, the barrier for the jump being highest for the polarizable water model. Our results highlight the role of polarizability in governing the dynamics of confined water and demonstrate that the inclusion of polarizability is necessary to obtain agreement with the results of ab initio simulations for the distributions of waiting and jump times. The SPC/E water model is found to predict various water properties in close agreement with the results of polarizable water models with much lower computational costs.