arXiv subjects

Ashutosh Kumar

Publications and source records attributed to Ashutosh Kumar.

At least 73 records · Page 4Linked to original sources

arXiv2021

Computing molecular excited states on a D-Wave quantum annealer

The possibility of using quantum computers for electronic structure calculations has opened up a promising avenue for computational chemistry. Towards this direction, numerous algorithmic advances have been made in the last five years. The potential of quantum annealers, which are the prototypes of adiabatic quantum computers, is yet to be fully explored. In this work, we demonstrate the use of a D-Wave quantum annealer for the calculation of excited electronic states of molecular systems. These simulations play an important role in a number of areas, such as photovoltaics, semiconductor technology and nanoscience. The excited states are treated using two methods, time-dependent Hartree-Fock (TDHF) and time-dependent density-functional theory (TDDFT), both within a commonly used Tamm-Dancoff approximation (TDA). The resulting TDA eigenvalue equations are solved on a D-Wave quantum annealer using the Quantum Annealer Eigensolver (QAE), developed previously. The method is shown to reproduce a typical basis set convergence on the example H$_2$ molecule and is also applied to several other molecular species. Characteristic properties such as transition dipole moments and oscillator strengths are computed as well. Three potential energy profiles for excited states are computed for NH$_3$ as a function of the molecular geometry. Similar to previous studies, the accuracy of the method is dependent on the accuracy of the intermediate meta-heuristic software called qbsolv.

physics.chem-ph↗

arXiv2021

Supersaturated ideals

A $σ$-ideal $\cal{I}$ on a set $X$ is supersaturated if for every family $\cal{F}$ of $\cal{I}$-positive sets with $|\cal{F}| < \mathrm{add}(\cal{I})$, there exists a countable set that meets every set in $\cal{F}$. We show that many well-known ccc forcings preserve supersaturation. We also show that the existence of supersaturated ideals is independent of ZFC plus "There exists an $ω_1$-saturated $σ$-ideal".

math.LO↗

arXiv2021

Effect of interface resistance on thermoelectric properties in (1-x)La$_{0.95}$Sr$_{0.05}$Co$_{0.95}$Mn$_{0.05}$O$_3$/(x)WC composite

In this study, the synergistic effect of the particle size of the dispersed phase and the interface thermal resistance (R$_{int}$) between the phases on the phonon thermal conductivity ($κ_{ph}$) of the (1-x)La$_{0.95}$Sr$_{0.05}$Co$_{0.95}$Mn$_{0.05}$O$_3$/(x)WC thermoelectric composite, is demonstrated. Further, the correlation between the R$_{int}$ and the Kapitza radius is discussed using the Bruggeman's asymmetrical model. In particular, the polycrystalline La$_{0.95}$Sr$_{0.05}$Co$_{0.95}$Mn$_{0.05}$O$_3$ sample is synthesized using a standard-solid state route. The presence of WC nanoparticle is confirmed from the electron microscopy images. Electrical conductivity ($σ$) increases, and the Seebeck coefficient ($α$) decreases with the increase in conducting WC volume fraction in the composite. The simultaneous increase in $σ$ and a decrease in $κ_{ph}$ with the WC volume fraction results in an increased figure of merit (zT) for (1-x)La$_{0.95}$Sr$_{0.05}$Co$_{0.95}$Mn$_{0.05}$O$_3$/(x)WC composite. A maximum zT $\sim$ 0.20 is obtained for (1-x)La$_{0.95}$Sr$_{0.05}$Co$_{0.95}$Mn$_{0.05}$O$_3$/(x)WC composite for x=0.010 at 463 K. The results obtained in the present study shows promise to design thermoelectric composites with desired phonon thermal conductivity considering the elastic properties between the phases.

cond-mat.mtrl-sci↗

arXiv2020

Thermal conductivity of PbTe-CoSb3 bulk polycrystalline composite: the role of microstructure and interface thermal resistance

Systematic experimental and theoretical research on the role of microstructure and interface thermal resistance on the thermal conductivity of the PbTe-CoSb3 bulk polycrystalline composite is presented. In particular, the correlation between the particle size of the dispersed phase and interface thermal resistance (R_{int}) on the phonon thermal conductivity (κ_{ph}) is discussed. With this aim, a series of PbTe-CoSb_3 polycrystalline composite materials with the different particle sizes of CoSb_3 was prepared. The structural (XRD) and microstructural analysis (SEM/EDXS) confirmed assumed chemical and phase compositions. The acoustic impedance difference (ΔZ) was determined from measured sound velocities in PbTe and CoSb_3 phases. The interface thermal resistance (R_{int}) was calculated using the Debye model and agrees with the experimental R_{int}. It is shown that the κ_{ph} of the composite may be reduced when the particle size of the dispersed phase (CoSb_3) is smaller than the critical value of ~230nm. This relationship was concluded to be crucial for controlling the heat transport phenomena in composite thermoelectric materials. The selection of the components with different elastic properties (acoustic impedance) and particle size smaller than the Kapitza radius leads to a new direction in the engineering of composite TE materials with designed thermal properties

cond-mat.mtrl-sci↗

arXiv2020

Transients generate memory and break hyperbolicity in stochastic enzymatic networks

The hyperbolic dependence of catalytic rate on substrate concentration is a classical result in enzyme kinetics, quantified by the celebrated Michaelis-Menten equation. The ubiquity of this relation in diverse chemical and biological contexts has recently been rationalized by a graph-theoretic analysis of deterministic reaction networks. Experiments, however, have revealed that "molecular noise" - intrinsic stochasticity at the molecular scale - leads to significant deviations from classical results and to unexpected effects like "molecular memory", i.e., the breakdown of statistical independence between turnover events. Here we show, through a new method of analysis, that memory and non-hyperbolicity have a common source in an initial, and observably long, transient peculiar to stochastic reaction networks of multiple enzymes. Networks of single enzymes do not admit such transients. The transient yields, asymptotically, to a steady-state in which memory vanishes and hyperbolicity is recovered. We propose new statistical measures, defined in terms of turnover times, to distinguish between the transient and steady states and apply these to experimental data from a landmark experiment that first observed molecular memory in a single enzyme with multiple binding sites. Our study shows that catalysis at the molecular level with more than one enzyme always contains a non-classical regime and provides insight on how the classical limit is attained.

q-bio.MN↗

arXiv2020

Colossal Seebeck coefficient in Aurivillius Phase-Perovskite Oxide Composite

We propose an inexpensive scalable approach for achieving extremely high values of Seebeck coefficient ($α$) by exploiting the natural superlattice structure in Aurivillius phase oxides. In particular, we report an $α\approx $ 319\,mV/K at 300\,K in a composite of Aurivillius phase compound SrBi$_4$Ti$_4$O$_{15}$ (as a matrix) and a perovskite phase material (e.g., La$_{0.7}$Sr$_{0.3}$MnO$_3$ or, La$_{0.7}$Sr$_{0.3}$CoO$_3$ as filler). Such a colossal value of $α$ can be attributed to contributions from the enhanced density of states due to the effective low dimensional character of Bi$_2$O$_2$ layer. The corresponding thermal conductivity ($κ$) and the electrical conductivity ($σ$) lies in the range 0.7 - 1.25 W/m-K and 10 - 100 $μ$S/m, respectively at 300\,K. Attributed to the high $α$ values, such oxide composites can be used as thermopile sensors and highly sensitive bolometric applications. We anticipate that the demonstration of colossal $α$ in oxide composites using a simple synthesis strategy also sets the stage for future material innovations for high temperature thermoelectric applications.

cond-mat.mtrl-sci↗

arXiv2020

Effective Thermal Conductivity of SrBi$_4$Ti$_4$O$_{15}$-La$_{0.7}$Sr$_{0.3}$MnO$_3$ Oxide composite: Role of Particle Size and Interface Thermal Resistance

We present a novel approach to reduce the thermal conductivity ($κ$) in thermoelectric composite materials using acoustic impedance mismatch and the Debye model. Also, the correlation between interface thermal resistance (R$_{int}$) and the particle size of the dispersed phase on the k of the composite is discussed. In particular, the $κ$ of an oxide composite which consists of a natural superlattice Aurivillius phase (SrBi$_4$Ti$_4$O$_{15}$) as a matrix and perovskite (La$_{0.7}$Sr$_{0.3}$MnO$_3$) as a dispersed phase is investigated. A significant reduction in the $κ$ of composite, even lower than the $κ$ of the matrix when the particle size of La$_{0.7}$Sr$_{0.3}$MnO$_3$ is smaller than the Kapitza radius (a$_K$) is observed, depicting that R$_{int}$ dominates for particle size lower than a$_K$ due to increased surface to volume ratio. The obtained results have the potential to provide new directions for engineering composite thermoelectric systems with desired thermal conductivity and promising in the field of energy harvesting.

cond-mat.mtrl-sci↗

arXiv2020

Explicitly correlated coupled cluster method for accurate treatment of open-shell molecules with hundreds of atoms

We present a near-linear scaling formulation of the explicitly-correlated coupled-cluster singles and doubles with perturbative triples method (CCSD(T)$_{\overline{\text{F12}}}$) for high-spin states of open-shell species. The approach is based on the conventional open-shell CCSD formalism [M. Saitow et al., J. Chem. Phys. 146, 164105 (2017)] utilizing the domain local pair-natural orbitals (DLPNO) framework. The use of spin-independent set of pair-natural orbitals ensures exact agreement with the closed-shell formalism reported previously, with only marginally impact on the cost (e.g. the open-shell formalism is only 1.5 times slower than the closed-shell counterpart for the $\text{C}_\text{160}\text{H}_{\text{322}}$ n-alkane, with the measured size complexity of $\approx1.2$). Evaluation of coupled-cluster energies near the complete-basis-set (CBS) limit for open-shell systems with more than 550 atoms and 5000 basis functions is feasible on a single multi-core computer in less than 3 days. The aug-cc-pVTZ DLPNO-CCSD(T)$_{\overline{\text{F12}}}$ contribution to the heat of formation for the 50 largest molecules among the 348 core combustion species benchmark set [J. Klippenstein et al., J. Phys. Chem. A 121, 6580 (2017)] had root-mean-square deviation (RMSD) from the extrapolated CBS CCSD(T) reference values of 0.3 kcal/mol. For a more challenging set of 50 reactions involving small closed- and open-shell molecules [G. Knizia et al., J. Chem. Phys. 130, 054104 (2009)] the aug-cc-pVQ(+d)Z DLPNO-CCSD(T)$_{\overline{\text{F12}}}$ yielded a RMSD of $\sim$0.4 kcal/mol with respect to the CBS CCSD(T) estimate.

physics.chem-ph↗

arXiv2020

Syntax-guided Controlled Generation of Paraphrases

Given a sentence (e.g., "I like mangoes") and a constraint (e.g., sentiment flip), the goal of controlled text generation is to produce a sentence that adapts the input sentence to meet the requirements of the constraint (e.g., "I hate mangoes"). Going beyond such simple constraints, recent works have started exploring the incorporation of complex syntactic-guidance as constraints in the task of controlled paraphrase generation. In these methods, syntactic-guidance is sourced from a separate exemplar sentence. However, these prior works have only utilized limited syntactic information available in the parse tree of the exemplar sentence. We address this limitation in the paper and propose Syntax Guided Controlled Paraphraser (SGCP), an end-to-end framework for syntactic paraphrase generation. We find that SGCP can generate syntax conforming sentences while not compromising on relevance. We perform extensive automated and human evaluations over multiple real-world English language datasets to demonstrate the efficacy of SGCP over state-of-the-art baselines. To drive future research, we have made SGCP's source code available

cs.CL↗

arXiv2018

Thermoelectric Properties of (1-x)LaCoO$_{3.x}$La$_{0.7}$Sr$_{0.3}$MnO$_3$ Composite

We report the thermoelectric (TE) properties of (1-x)LaCoO3.xLa0.7Sr0.3MnO3 (0 < x < 0.10) composite in a temperature range 320-800 K. Addition of La0.7Sr0.3MnO3 to LaCoO3 in small amount (5 weight %) improves the overall Seebeck coefficient (α) at higher temperatures. The electrical conductivity, however, decreases due to a decrease in carrier concentration of the composite. The decrease in electrical conductivity of the composite at high temperature may be attributed to the insulating nature of the LSMO above room temperature. Thermal conductivity (\k{appa}) of all the samples increases with an increase in the temperature but decreases with increasing LSMO content. We also report the local variation of the Seebeck coefficient across the composite samples measured using a precision Seebeck measurement system. A maximum value of 0.09 for the figure of merit (ZT) is obtained for 0.95LaCoO3.0.05La0.7Sr0.3MnO3 at 620 K which is significantly higher than the ZT of either of LaCoO3 or La0.7Sr0.3MnO3 at 620 K. This suggests the potential for enhancement of operating temperatures of hitherto well known low-temperature thermoelectric materials through suitable compositing approach.

cond-mat.mtrl-sci↗

arXiv2018

On some variants of the club principle

We study some asymptotic variants of the club principle. Along the way, we construct some forcings and use them to separate several of these principles

math.LO↗

arXiv2018

eCommerceGAN : A Generative Adversarial Network for E-commerce

E-commerce companies such as Amazon, Alibaba and Flipkart process billions of orders every year. However, these orders represent only a small fraction of all plausible orders. Exploring the space of all plausible orders could help us better understand the relationships between the various entities in an e-commerce ecosystem, namely the customers and the products they purchase. In this paper, we propose a Generative Adversarial Network (GAN) for orders made in e-commerce websites. Once trained, the generator in the GAN could generate any number of plausible orders. Our contributions include: (a) creating a dense and low-dimensional representation of e-commerce orders, (b) train an ecommerceGAN (ecGAN) with real orders to show the feasibility of the proposed paradigm, and (c) train an ecommerce-conditional-GAN (ec^2GAN) to generate the plausible orders involving a particular product. We propose several qualitative methods to evaluate ecGAN and demonstrate its effectiveness. The ec^2GAN is used for various kinds of characterization of possible orders involving a product that has just been introduced into the e-commerce system. The proposed approach ec^2GAN performs significantly better than the baseline in most of the scenarios.

cs.LG↗

arXiv2016

Broadband excitation by method of double sweep

The paper describes the design of broadband excitation pulses in high resolution NMR by method of double sweep. We first show the design of a pulse sequence that produces broadband excitation to the equator of Bloch sphere with phase linearly dispersed as frequency. We show how this linear dispersion can then be refocused by nesting free evolution between two adiabatic inversions (sweeps). We then show how this construction can be generalized to exciting arbitrary large bandwidths without increasing the peak rf-amplitude and by incorporating more adiabatic sweeps. Finally, we show how the basic design can then be modified to give a broadband $x$ rotation over arbitrary large bandwidth and with limited rf-amplitude. Experimental excitation profiles for the residual HDO signal in a sample of $99.5\%$ D$_2$0 are displayed as a function of resonance offset. Application of the excitation is shown for $^{13}$C excitation in a labelled sample of Alanine.

quant-ph↗

arXiv2016

Emergence of Dynamic Cooperativity in the Stochastic Kinetics of Fluctuating Enzymes

Dynamic cooperativity in monomeric enzymes is characterized in terms of a non-Michaelis-Menten kinetic behaviour. The latter is believed to be associated with mechanisms that include multiple reaction pathways due to enzymatic conformational fluctuations. Recent advances in single-molecule fluorescence spectroscopy have provided new fundamental insights on the possible mechanisms underlying reactions catalyzed by fluctuating enzymes. Here, we present a bottom-up approach to understand enzyme turnover kinetics at physiologically relevant mesoscopic concentrations informed by mechanisms extracted from single-molecule stochastic trajectories. The stochastic approach, presented here, shows the emergence of dynamic cooperativity in terms of a slowing down of the Michaelis-Menten (MM) kinetics resulting in negative cooperativity. For fewer enzymes, dynamic cooperativity emerges due to the combined effects of enzymatic conformational fluctuations and molecular discreteness. The increase in the number of enzymes, however, suppresses the effect of enzymatic conformational fluctuations such that dynamic cooperativity emerges solely due to the discrete changes in the number of reacting species. These results confirm that the turnover kinetics of fluctuating enzyme based on the parallel-pathway MM mechanism switches over to the single-pathway MM mechanism with the increase in the number of enzymes. For large enzyme numbers, convergence to the exact MM equation occurs in the limit of very high substrate concentration as the stochastic kinetics approaches the deterministic behaviour.

physics.chem-ph↗

arXiv2016

Magnetism in La$_{0.7}$Sr$_{0.3}$Mn$_{1-x}$Co$_x$O$_3$ ($0 \leq x \leq 1$)

We study the structural and magnetic properties of La$_{0.7}$Sr$_{0.3}$Mn$_{1-x}$Co$_x$O$_3$ ($0 \leq x \leq 1$). Rietveld refinement of X-ray Diffraction (XRD) pattern suggests phase purity of the polycrystalline samples with R$\bar{3}$c space group. Interplay of Ferromagnetic (FM) and Antiferromagnetic (AFM) interaction upon Co substitution at Mn site in La$_{0.7}$Sr$_{0.3}$MnO$_3$ is evident from magnetic measurements. There is an optimal cobalt substitution at which the coercive field is maximum.

cond-mat.mtrl-sci↗

arXiv2016

Extreme Sensitivity of Magnetic Properties on the Synthesis Routes in La$_{0.7}$Sr$_{0.3}$MnO$_3$

La$_{0.7}$Sr$_{0.3}$MnO$_3$ polycrystalline samples have been prepared using different synthesis routes. X-ray Diffraction (XRD) confirms that the samples are of single phase with R$\bar{3}$c space group. The surface morphology and particle size has been measured using Field Emission Scanning Electron Microscopy (FESEM). Magnetic measurement shows that the magnetization in the materials are affected by low crystallite size which destroys the spin ordering due to strain at grain boundaries and in turn also lead to reduction in magnetization as well as an enhanced coercivity in the material.

cond-mat.mtrl-sci↗

arXiv2015

Parallel versus off-pathway Michaelis-Menten mechanism for single-enzyme kinetics of a fluctuating enzyme

Recent fluorescence spectroscopy measurements of the turnover time distribution of single-enzyme turnover kinetics of $β$-galactosidase provide evidence of Michaelis-Menten kinetics at low substrate concentration. However, at high substrate concentrations, the dimensionless variance of the turnover time distribution shows systematic deviations from the Michaelis-Menten prediction. This difference is attributed to conformational fluctuations in both the enzyme and the enzyme-substrate complex and to the possibility of both parallel and off-pathway kinetics. Here, we use the chemical master equation to model the kinetics of a single fluctuating enzyme that can yield a product through either parallel or off-pathway mechanisms. An exact expression is obtained for the turnover time distribution from which the mean turnover time and randomness parameters are calculated. The parallel and off-pathway mechanisms yield strikingly different dependences of the mean turnover time and the randomness parameter on the substrate concentration. In the parallel mechanism, the distinct contributions of enzyme and enzyme-substrate fluctuations are clearly discerned from the variation of the randomness parameter with substrate concentration. From these general results we conclude that an off-pathway mechanism, with substantial enzyme-substrate fluctuations, is needed to rationalize the experimental findings of single-enzyme turnover kinetics of $β$-galactosidase.

physics.chem-ph↗

arXiv2013

Electron-Hole Pair Generation in SiC High-Temperature Alpha Particle Detectors

We demonstrate alpha-particle detection in an n-type 4H-SiC Schottky diode detector up to an unprecedented temperature of 500 °C using an Am-241 disc source. The measured spectra were used to calculate the electron-hole pair creation energy in 4H-SiC and its non-bandgap contribution, which are both found to decrease with increasing temperature. The full width at half maximum (FWHM) of the measured alpha-energy peaks was found to increase exponentially with temperature due to an exponential increase of leakage current. For our measurement system, above 300 °C, where the leakage current was 10-6 A, this increase exceeded the FWHM at room temperature.

physics.ins-det↗