Ab initio, DFT and transition state theory calculations on 1,2-HF, HCI and CIF elimination reactions from CH2F-CH2Cl

This paper reports ab intio, DFT and transition state theory (TST) calculations on HF, HCI and CIF elimination reactions from CH2Cl-CH2F molecule. Both the ground state and the transition state for HX elimination reactions have been optimized at HF, MP2 and DFT calculations with 6-31G*, 6-31G** and 6-311++G** basis sets. In addition, CCSD(T) single point calculations were carried out with MP2/6-311++G** optimized geometry for more accurate determination of the energies of the minima and transition state, compared to the other methods employed here. Classical barriers are converted to Arrhenius activation energy by TST calculations for comparisons with experimental results. The pre-exponential factors, A, calculated at all levels of theory are significantly larger than the experimental values. For activation energy, E-a DFT gives good results for HF elimination, within 4-8 W mol(-1) from experimental values. None of the methods employed, including CCSD(T), give comparable results for HCI elimination reactions. However, rate constants calculated by CCSD(T) method are in very good agreement with experiment for HCI elimination and they are in reasonable agreement for HF elimination reactions. Due to the strong correlation between A and E., the rate constants could be fit to a lower A and E-a (as given by experimental fitting, corresponding to a tight TS) or to larger A and E-a (as given by high level ab initio calculations, corresponding to a loose TS). The barrier for CIF elimination is determined to be 607 U mol(-1) at HF level and it is unlikely to be important for CH2FCH2Cl. Results for other CH2X-CH2Y (X,Y = F/Cl) are included for comparison.

A waveguide problem involving a thick iris in the theory of electromagnetism

The problem of electromagnetic wave propagation in a rectangular waveguide containing a thick iris is considered for its complete solution by reducing it to two suitable integral equations, one of which is of the first kind and the other is of the second kind. These integral equations are solved approximately, by using truncated Fourier series for the unknown functions. The reflection coefficient is computed numerically from the two integral equation approaches, and almost the same numerical results are obtained. This is also depicted graphically against the wave number and compared with thin iris results, which are computed by using complementary formulations coupled with Galerkin approximations. While the reflection coefficient for a thin iris steadily increases with the wave number, for a thick iris it fluctuates and zero reflection occurs. The number of zeros of the reflection coefficient for a thick iris increases with the thickness. Thus a thick iris becomes completely transparent for some discrete wave numbers. This phenomenon may be significant in the modelling of rectangular waveguides.

Interference Alignment as a Tool in Network Coding as Applied to Distributed Storage

In this paper, we outline an approach to the task of designing network codes in a non-multicast setting. Our approach makes use of the concept of interference alignment. As an example, we consider the distributed storage problem where the data is stored across the network in n nodes and where a data collector can recover the data by connecting to any k of the n nodes and where furthermore, upon failure of a node, a new node can replicate the data stored in the failed node while minimizing the repair bandwidth.

On the Compressibility of non-Abelian-Group Sources in a Distributed Source Coding Setting

We consider the problem of compression of a non-Abelian source.This is motivated by the problem of distributed function computation,where it is known that if one is only interested in computing a function of several sources, then one can often improve upon the compression rate required by the Slepian-Wolf bound. Let G be a non-Abelian group having center Z(G). We show here that it is impossible to compress a source with symbols drawn from G when Z(G) is trivial if one employs a homomorphic encoder and a typical-set decoder.We provide achievable upper bounds on the minimum rate required to compress a non-Abelian group with non-trivial center. Also, in a two source setting, we provide achievable upper bounds for compression of any non-Abelian group, using a non-homomorphic encoder.

Theory of Gas Hydrates: Effect of the Approximation of Rigid Water Lattice

One of the assumptions of the van der Waals and Platteeuw theory for gas hydrates is that the host water lattice is rigid and not distorted by the presence of guest molecules. In this work, we study the effect of this approximation on the triple-point lines of the gas hydrates. We calculate the triple-point lines of methane and ethane hydrates via Monte Carlo molecular simulations and compare the simulation results with the predictions of van der Waals and Platteeuw theory. Our study shows that even if the exact intermolecular potential between the guest molecules and water is known, the dissociation temperatures predicted by the theory are significantly higher. This has serious implications to the modeling of gas hydrate thermodynamics, and in spite of the several impressive efforts made toward obtaining an accurate description of intermolecular interactions in gas hydrates, the theory will suffer from the problem of robustness if the issue of movement of water molecules is not adequately addressed.

A Low-Complexity, Full-Rate, Full-Diversity 2x2 STBC with Golden Code's Coding Gain

This paper presents a low-ML-decoding-complexity, full-rate, full-diversity space-time block code (STBC) for a 2 transmit antenna, 2 receive antenna multiple-input multipleoutput (MIMO) system, with coding gain equal to that of the best and well known Golden code for any QAM constellation.Recently, two codes have been proposed (by Paredes, Gershman and Alkhansari and by Sezginer and Sari), which enjoy a lower decoding complexity relative to the Golden code, but have lesser coding gain. The 2 × 2 STBC presented in this paper has lesser decoding complexity for non-square QAM constellations,compared with that of the Golden code, while having the same decoding complexity for square QAM constellations. Compared with the Paredes-Gershman-Alkhansari and Sezginer-Sari codes, the proposed code has the same decoding complexity for nonrectangular QAM constellations. Simulation results, which compare the codeword error rate (CER) performance, are presented.

Network Coding for TCP Throughput Enhancement over a Multi-Hop wireless Network

The poor performance of TCP over multi-hop wireless networks is well known. In this paper we explore to what extent network coding can help to improve the throughput performance of TCP controlled bulk transfers over a chain topology multi-hop wireless network. The nodes use a CSMA/ CA mechanism, such as IEEE 802.11’s DCF, to perform distributed packet scheduling. The reverse flowing TCP ACKs are sought to be X-ORed with forward flowing TCP data packets. We find that, without any modification to theMAC protocol, the gain from network coding is negligible. The inherent coordination problem of carrier sensing based random access in multi-hop wireless networks dominates the performance. We provide a theoretical analysis that yields a throughput bound with network coding. We then propose a distributed modification of the IEEE 802.11 DCF, based on tuning the back-off mechanism using a feedback approach. Simulation studies show that the proposed mechanism when combined with network coding, improves the performance of a TCP session by more than 100%.

Novel Algorithm for estimation of Swell Pressure of Fine Grained Soils Based on Diffuse Double Layer (DDL) Theory

Use of engineered landfills for the disposal of industrial wastes is currently a common practice. Bentonite is attracting a greater attention not only as capping and lining materials in landfills but also as buffer and backfill materials for repositories of high-level nuclear waste around the world. In the design of buffer and backfill materials, it is important to know the swelling pressures of compacted bentonite with different electrolyte solutions. The theoretical studies on swell pressure behaviour are all based on Diffuse Double Layer (DDL) theory. To establish a relation between the swell pressure and void ratio of the soil, it is necessary to calculate the mid-plane potential in the diffuse part of the interacting ionic double layers. The difficulty in these calculations is the elliptic integral involved in the relation between half space distance and mid plane potential. Several investigators circumvented this problem using indirect methods or by using cumbersome numerical techniques. In this work, a novel approach is proposed for theoretical estimations of swell pressures of fine-grained soil from the DDL theory. The proposed approach circumvents the complex computations in establishing the relationship between mid-plane potential and diffused plates’ distances in other words, between swell pressure and void ratio.

Distributed Source Coding for Sensor Data Model and Estimation of Cluster Head Errors Using Bayesian and K-Near Neighborhood Classifiers in Deployment of Dense Wireless Sensor Networks

The lifetime calculation of large dense sensor networks with fixed energy resources and the remaining residual energy have shown that for a constant energy resource in a sensor network the fault rate at the cluster head is network size invariant when using the network layer with no MAC losses.Even after increasing the battery capacities in the nodes the total lifetime does not increase after a max limit of 8 times. As this is a serious limitation lots of research has been done at the MAC layer which allows to adapt to the specific connectivity, traffic and channel polling needs for sensor networks. There have been lots of MAC protocols which allow to control the channel polling of new radios which are available to sensor nodes to communicate. This further reduces the communication overhead by idling and sleep scheduling thus extending the lifetime of the monitoring application. We address the two issues which effects the distributed characteristics and performance of connected MAC nodes. (1) To determine the theoretical minimum rate based on joint coding for a correlated data source at the singlehop, (2a) to estimate cluster head errors using Bayesian rule for routing using persistence clustering when node densities are the same and stored using prior probability at the network layer, (2b) to estimate the upper bound of routing errors when using passive clustering were the node densities at the multi-hop MACS are unknown and not stored at the multi-hop nodes a priori. In this paper we evaluate many MAC based sensor network protocols and study the effects on sensor network lifetime. A renewable energy MAC routing protocol is designed when the probabilities of active nodes are not known a priori. From theoretical derivations we show that for a Bayesian rule with known class densities of omega1, omega2 with expected error P* is bounded by max error rate of P=2P* for single-hop. We study the effects of energy losses using cross-layer simulation of - large sensor network MACS setup, the error rate which effect finding sufficient node densities to have reliable multi-hop communications due to unknown node densities. The simulation results show that even though the lifetime is comparable the expected Bayesian posterior probability error bound is close or higher than Pges2P*.

Co-ordinate interleaved distributed space-time coding for two-antenna relay networks

Distributed space time coding for wireless relay networks where the source, the destination and the relays have multiple antennas have been studied by Jing and Hassibi. In this set up, the transmit and the receive signals at different antennas of the same relay are processed and designed independently, even though the antennas are colocated. In this paper, a wireless relay network with single antenna at the source and the destination and two antennas at each of the R relays is considered. In the first phase of the two-phase transmission model, a T -length complex vector is transmitted from the source to all the relays. At each relay, the inphase and quadrature component vectors of the received complex vectors at the two antennas are interleaved before processing them. After processing, in the second phase, a T x 2R matrix codeword is transmitted to the destination. The collection of all such codewords is called Co-ordinate interleaved distributed space-time code (CIDSTC). Compared to the scheme proposed by Jing-Hassibi, for T ges AR, it is shown that while both the schemes give the same asymptotic diversity gain, the CIDSTC scheme gives additional asymptotic coding gain as well and that too at the cost of negligible increase in the processing complexity at the relays.