Intra-molecular hydrogen bonding with organic fluorine in the solution state: Deriving evidence by a two dimensional NMR experiment

The direct evidence for the existence of intra-molecular C-F center dot center dot center dot H-N hydrogen bond in organofluorine molecules, in the liquid state, is derived using NMR spectroscopy by the detection of long range interactions among fluorine, nitrogen and hydrogen atoms. The present study reports the determination of the relative signs and magnitudes of through space and through bond couplings to draw unambiguous evidence on the existence of weak molecular interactions involving organic fluorine. It is a simple, easy to implement, N-15 natural abundant two dimensional heteronuclear N-15-H-1 double quantum-single quantum correlation experiment. The existence of intra-molecular hydrogen bond is conclusively established in the investigated molecules. (C) 2011 Elsevier B.V. All rights reserved.

Online Computation of Hysteresis Boundary for Constant Switching Frequency Current-Error Space-Vector-Based Hysteresis Controller for VSI-Fed IM Drives

This paper proposes a current-error space-vector-based hysteresis controller with online computation of boundary for two-level inverter-fed induction motor (IM) drives. The proposed hysteresis controller has got all advantages of conventional current-error space-vector-based hysteresis controllers like quick transient response, simplicity, adjacent voltage vector switching, etc. Major advantage of the proposed controller-based voltage-source-inverters-fed drive is that phase voltage frequency spectrum produced is exactly similar to that of a constant switching frequency space-vector pulsewidth modulated (SVPWM) inverter. In this proposed hysteresis controller, stator voltages along alpha- and beta-axes are estimated during zero and active voltage vector periods using current errors along alpha- and beta-axes and steady-state model of IM. Online computation of hysteresis boundary is carried out using estimated stator voltages in the proposed hysteresis controller. The proposed scheme is simple and capable of taking inverter upto six-step-mode operation, if demanded by drive system. The proposed hysteresis-controller-based inverter-fed drive scheme is experimentally verified. The steady state and transient performance of the proposed scheme is extensively tested. The experimental results are giving constant frequency spectrum for phase voltage similar to that of constant frequency SVPWM inverter-fed drive.

State Dependent Attempt Rate modeling of single cell IEEE 802.11 WLANs with homogeneous nodes and Poisson packet arrivals

We study a State Dependent Attempt Rate (SDAR) approximation to model M queues (one queue per node) served by the Carrier Sense Multiple Access with Collision Avoidance (CSMA/CA) protocol as standardized in the IEEE 802.11 Distributed Coordination Function (DCF). The approximation is that, when n of the M queues are non-empty, the (transmission) attempt probability of each of the n non-empty nodes is given by the long-term (transmission) attempt probability of n saturated nodes. With the arrival of packets into the M queues according to independent Poisson processes, the SDAR approximation reduces a single cell with non-saturated nodes to a Markovian coupled queueing system. We provide a sufficient condition under which the joint queue length Markov chain is positive recurrent. For the symmetric case of equal arrival rates and finite and equal buffers, we develop an iterative method which leads to accurate predictions for important performance measures such as collision probability, throughput and mean packet delay. We replace the MAC layer with the SDAR model of contention by modifying the NS-2 source code pertaining to the MAC layer, keeping all other layers unchanged. By this model-based simulation technique at the MAC layer, we achieve speed-ups (w.r.t. MAC layer operations) up to 5.4. Through extensive model-based simulations and numerical results, we show that the SDAR model is an accurate model for the DCF MAC protocol in single cells. (C) 2012 Elsevier B.V. All rights reserved.

Multilevel Dodecagonal Voltage Space Vector Generation using Flying Capacitor topology for Induction motor drives

In this paper, a multilevel flying capacitor inverter topology suitable for generating multilevel dodecagonal space vectors for an induction motor drive, is proposed. Because of the dodecagonal space vectors, it has increased modulation range with the absence of all 6n +/- 1, (n=odd) harmonics in the phase voltage and currents. The topology, realized by flying capacitor three level inverters feeding an open-end winding induction motor, does not suffer the neutral point voltage imbalance issues seen in NPC inverters and the capacitors have inherent charge-balancing capability with PWM control using switching state redundancies. Furthermore, the proposed technique uses lesser number of power supplies compared to cascaded H-bridge or NPC based dodecagonal schemes and has better ride-through capability. Finally, the voltage control is obtained through a simple carrier-based space vector PWM scheme implemented on a DSP.

Distributed Space Time Coding for Wireless Two-Way Relaying

We consider the wireless two-way relay channel, in which two-way data transfer takes place between the end nodes with the help of a relay. For the Denoise-And-Forward (DNF) protocol, it was shown by Koike-Akino et al. that adaptively changing the network coding map used at the relay greatly reduces the impact of Multiple Access Interference at the relay. The harmful effect of the deep channel fade conditions can be effectively mitigated by proper choice of these network coding maps at the relay. Alternatively, in this paper we propose a Distributed Space Time Coding (DSTC) scheme, which effectively removes most of the deep fade channel conditions at the transmitting nodes itself without any CSIT and without any need to adaptively change the network coding map used at the relay. It is shown that the deep fades occur when the channel fade coefficient vector falls in a finite number of vector subspaces of, which are referred to as the singular fade subspaces. DSTC design criterion referred to as the singularity minimization criterion under which the number of such vector subspaces are minimized is obtained. Also, a criterion to maximize the coding gain of the DSTC is obtained. Explicit low decoding complexity DSTC designs which satisfy the singularity minimization criterion and maximize the coding gain for QAM and PSK signal sets are provided. Simulation results show that at high Signal to Noise Ratio, the DSTC scheme provides large gains when compared to the conventional Exclusive OR network code and performs better than the adaptive network coding scheme.

Engagement of CF3 Group in N-H center dot center dot center dot F-C Hydrogen Bond in the Solution State: NMR Spectroscopy and MD Simulation Studies

Unambiguous evidence for the engagement of CF3 group in N-H center dot center dot center dot F-C hydrogen bond in a low polarity solvent, the first observation of its kind, is reported. The presence of such weak molecular interactions in the solution state is convincingly established by one and two-dimensional H-1, F-19, and natural abundant N-15 NMR spectroscopic studies. The strong and direct evidence is derived by the observation of through-space couplings, such as, (1h)J(FH), (1h)J(FN), and (2h)J(FF), where the spin polarization is transmitted through hydrogen bond. In an interesting example of a molecule containing two CF3 groups getting simultaneously involved in hydrogen bond, where hydrogen bond mediated couplings are not reflected in the NMR spectrum, F-19-F-19 NOESY experiment yielded confirmatory evidence. Significant deviations in the strengths of (1)J(NH), variable temperature, and the solvent induced perturbations yielded additional support. The NMR results are corroborated by both DFT calculations and MD simulations, where the quantitative information on different ways of involvement of fluorine in two and three centered hydrogen bonds, their percentage of occurrences, and geometries have been obtained. The hydrogen bond interaction energies have also been calculated.

Adaptive constellation rotation scheme for two-user fading MAC with quantized fade state feedback

With no Channel State Information (CSI) at the users, transmission over the two-user Gaussian Multiple Access Channel with fading and finite constellation at the input, will have high error rates due to multiple access interference (MAI). However, perfect CSI at the users is an unrealistic assumption in the wireless scenario, as it would involve extremely large feedback overheads. In this paper we propose a scheme which removes the adverse effect of MAI using only quantized knowledge of fade state at the transmitters such that the associated overhead is nominal. One of the users rotates its constellation relative to the other without varying the transmit power to adapt to the existing channel conditions, in order to meet certain predetermined minimum Euclidean distance requirement in the equivalent constellation at the destination. The optimal rotation scheme is described for the case when both the users use symmetric M-PSK constellations at the input, where M = 2(gimel), gimel being a positive integer. The strategy is illustrated by considering the example where both the users use QPSK signal sets at the input. The case when the users use PSK constellations of different sizes is also considered. It is shown that the proposed scheme has considerable better error performance compared to the conventional non-adaptive scheme, at the cost of a feedback overhead of just log log(2) (M-2/8 - M/4 + 2)] + 1 bits, for the M-PSK case.

Minimum uncertainty and entanglement

We address the question, does a system A being entangled with another system B, put any constraints on the Heisenberg uncertainty relation (or the Schrodinger-Robertson inequality)? We find that the equality of the uncertainty relation cannot be reached for any two noncommuting observables, for finite dimensional Hilbert spaces if the Schmidt rank of the entangled state is maximal. One consequence is that the lower bound of the uncertainty relation can never be attained for any two observables for qubits, if the state is entangled. For infinite-dimensional Hilbert space too, we show that there is a class of physically interesting entangled states for which no two noncommuting observables can attain the minimum uncertainty equality.

Tradeoff of average service cost and average delay for the state dependent M/M/1 queue

The optimal tradeoff between average service cost rate and average delay, is addressed for a M/M/1 queueing model with queue-length dependent service rates, chosen from a finite set. We provide an asymptotic characterization of the minimum average delay, when the average service cost rate is a small positive quantity V more than the minimum average service cost rate required for stability. We show that depending on the value of the arrival rate, the assumed service cost rate function, and the possible values of the service rates, the minimum average delay either a) increases only to a finite value, b) increases without bound as log(1/V), or c) increases without bound as 1/V, when V down arrow 0. We apply the analysis to a flow-level resource allocation model for a wireless downlink. We also investigate the asymptotic tradeoff for a sequence of policies which are obtained from an approximate fluid model for the M/M/1 queue.

Quantum entropic ambiguities: Ethylene

In a quantum system, there may be many density matrices associated with a state on an algebra of observables. For each density matrix, one can compute its entropy. These are, in general, different. Therefore, one reaches the remarkable possibility that there may be many entropies for a given state R. Sorkin (private communication)]. This ambiguity in entropy can often be traced to a gauge symmetry emergent from the nontrivial topological character of the configuration space of the underlying system. It can also happen in finite-dimensional matrix models. In the present work, we discuss this entropy ambiguity and its consequences for an ethylene molecule. This is a very simple and well-known system, where these notions can be put to tests. Of particular interest in this discussion is the fact that the change of the density matrix with the corresponding entropy increase drives the system towards the maximally disordered state with maximum entropy, where Boltzman's formula applies. Besides its intrinsic conceptual interest, the simplicity of this model can serve as an introduction to a similar discussion of systems such as colored monopoles and the breaking of color symmetry.

MINIMUM UNCERTAINTY AND ENTANGLEMENT

We address the question, does a system A being entangled with another system B, put any constraints on the Heisenberg uncertainty relation (or the Schrodinger-Robertson inequality)? We find that the equality of the uncertainty relation cannot be reached for any two noncommuting observables, for finite dimensional Hilbert spaces if the Schmidt rank of the entangled state is maximal. One consequence is that the lower bound of the uncertainty relation can never be attained for any two observables for qubits, if the state is entangled. For infinite-dimensional Hilbert space too, we show that there is a class of physically interesting entangled states for which no two noncommuting observables can attain the minimum uncertainty equality.

An adaptive modulation scheme for two-user fading MAC with quantized fade state feedback

For transmission over the two-user Gaussian Multiple Access Channel with fading and finite constellation at the inputs, we propose a scheme which uses only quantized knowledge of fade state at users with the feedback overhead being nominal. One of the users rotates its constellation without varying the transmit power to adapt to the existing channel conditions, in order to meet certain pre-determined minimum Euclidean distance requirement in the equivalent constellation at the destination. The optimal modulation scheme has been described for the case when both the users use symmetric M-PSK constellations at the input, where M = 2λ, λ being a positive integer. The strategy has been illustrated by considering examples where both the users use QPSK signal set at the input. It is shown that the proposed scheme has considerable better error performance compared to the conventional non-adaptive scheme, at the cost of a feedback overhead of just [log2 (M2/8 - M/4 + 2)] + 1 bits, for the M-PSK case.

Improved perfect space-time block codes

Perfect space-time block codes (STBCs) are based on four design criteria-full-rateness, nonvanishing determinant, cubic shaping, and uniform average transmitted energy per antenna per time slot. Cubic shaping and transmission at uniform average energy per antenna per time slot are important from the perspective of energy efficiency of STBCs. The shaping criterion demands that the generator matrix of the lattice from which each layer of the perfect STBC is carved be unitary. In this paper, it is shown that unitariness is not a necessary requirement for energy efficiency in the context of space-time coding with finite input constellations, and an alternative criterion is provided that enables one to obtain full-rate (rate of complex symbols per channel use for an transmit antenna system) STBCs with larger normalized minimum determinants than the perfect STBCs. Further, two such STBCs, one each for 4 and 6 transmit antennas, are presented and they are shown to have larger normalized minimum determinants than the comparable perfect STBCs which hitherto had the best-known normalized minimum determinants.

Energy Loss in the Impact of Elastic Spheres on a Rigid Half-Space in Presence of Adhesion

Adhesion can cause energy losses in asperities or particles coming into dynamic contact resulting in frictional dissipation, even if the deformation occurring is purely elastic. Such losses are of special significance in impact of nanoparticles and friction between surfaces under low contact pressure to hardness ratio. The objective of this work is to study the effect of adhesion during the normal impact of elastic spheres on a rigid half-space, with an emphasis on understanding the mechanism of energy loss. We use finite element method for modeling the impact phenomenon, with the adhesion due to van der Waals force and the short-range repulsion included as body forces distributed over the volume of the sphere. This approach, in contrast with commonly used surface force approximation, helps to model the interactions in a more precise way. We find that the energy loss in impact of elastic spheres is negligible unless there are adhesion-induced instabilities. Significant energy loss through elastic stress waves occurs due to jump-to-contact and jump-out-of-contact instabilities and can even result in capture of the elastic sphere on the half-space.

Photophysical, electrochemical and solid state properties of diketopyrrolopyrrole based molecular materials: importance of the donor group

Diketopyrrolopyrrole (DPP) based molecular semiconductors have emerged as promising materials for high performance active layers in organic solar cells. It is imperative to comprehend the origin of such a property by investigating the fundamental structure property correlation. In this report we have investigated the role of the donor group in DPP based donor-acceptor- donor (D-A-D) structure to govern the solid state, photophysical and electrochemical properties. We have prepared three derivatives of DPP with varying strengths of the donor groups, such as phenyl (PDPP-Hex), thiophene (TDPP-Hex) and selenophene (SeDPP-Hex). The influence of the donor units on the solid state packing was studied by single crystal X-ray diffraction. The photophysical, electrochemical and density functional theory ( DFT) results were combined to elucidate the structural and electronic properties of three DPP derivatives. We found that these DPP derivatives crystallized in the monoclinic space group P21/c and show herringbone packing in the crystal lattice. The derivatives exhibit weak p-p stacking interactions as two neighboring molecules slip away from each other with varied torsional angles at the donor units. The high torsional angle of 32 degrees ( PDPP-Hex) between the phenyl and lactam ring results in weak intramolecular interactions between the donor and acceptor, while TDPP-Hex and SeDPP-Hex show lower torsional angles of 9 degrees and 12 degrees with a strong overlap between the donor and acceptor units. The photophysical properties reveal that PDPP-Hex exhibits a high Stokes shift of 0.32 eV and SeDPP- Hex shows a high molar absorption co-efficient of 33 600 L mol -1 1 cm -1 1 with a low band gap of similar to 2.2 eV. The electrochemical studies of SeDPP- Hex indicate the pronounced effect of selenium in stabilizing the LUMO energy levels and this further emphasizes the importance of chalcogens in developing new n-type organic semiconductors for optoelectronic devices.