arXiv subjects

Sandeep Sharma

Publications and source records attributed to Sandeep Sharma.

70 records · Page 4Linked to original sources

arXiv2017

Modeling the impact of rain on population exposed to air pollution

Environmental pollution, comprising of air, water and soil have emerged as a serious problem in past two decades. The air pollution is caused by contamination of air due to various natural and anthropogenic activities. The growing air pollution has diverse adverse effects on human health and other living species. However, a significant reduction in the concentration of air pollutants has been observed during the rainy season. Recently, a number of studies have been performed to understand the mechanism of removal of air pollutants due to the rain. These studies have found that rain is helpful in removing many air pollutants from the environment. In this paper, we proposed a mathematical model to investigate the role of rain in removal of air pollutants and its subsequent impacts on human population.

physics.ao-ph↗

arXiv2017

Semistochastic Heat-bath Configuration Interaction method: selected configuration interaction with semistochastic perturbation theory

We extend the recently proposed heat-bath configuration interaction (HCI) method [Holmes, Tubman, Umrigar, J. Chem. Theory Comput. 12, 3674 (2016)], by introducing a semistochastic algorithm for performing multireference Epstein-Nesbet perturbation theory, in order to completely eliminate the severe memory bottleneck of the original method. The proposed algorithm has several attractive features. First, there is no sign problem that plagues several quantum Monte Carlo methods. Second, instead of using Metropolis-Hastings sampling, we use the Alias method to directly sample determinants from the reference wavefunction, thus avoiding correlations between consecutive samples. Third, in addition to removing the memory bottleneck, semistochastic HCI (SHCI) is faster than the deterministic variant for many systems if a stochastic error of 0.1 mHa is acceptable. Fourth, within the SHCI algorithm one can trade memory for a modest increase in computer time. Fifth, the perturbative calculation is embarrassingly parallel. The SHCI algorithm extends the range of applicability of the original algorithm, allowing us to calculate the correlation energy of very large active spaces. We demonstrate this by performing calculations on several first row dimers including F2 with an active space of (14e, 108o), Mn-Salen cluster with an active space of (28e, 22o), and Cr2 dimer with up to a quadruple-zeta basis set with an active space of (12e, 190o). For these systems we were able to obtain better than 1 mHa accuracy with a wall time of merely 55 seconds, 37 seconds, and 56 minutes on 1, 1, and 4 nodes, respectively.

physics.chem-ph↗

arXiv2017

The Python-based Simulations of Chemistry Framework (PySCF)

PySCF is a general-purpose electronic structure platform designed from the ground up to emphasize code simplicity, both to aid new method development, as well as for flexibility in computational workflow. The package provides a wide range of tools to support simulations of finite size systems, extended systems with periodic boundary conditions, low dimensional periodic systems, and custom Hamiltonians, using mean-field and post-mean-field methods with standard Gaussian basis functions. To ensure easy of extensibility, PySCF uses the Python language to implement almost all its features, while computationally critical paths are implemented with heavily optimized C routines. Using this combined Python/C implementation, the package is as efficient as the best existing C or Fortran based quantum chemistry programs. In this paper we document the capabilities and design philosophy of the current version of the PySCF package.

physics.chem-ph↗

arXiv2016

Stochastic multi-reference perturbation theory with application to linearized coupled cluster method

In this article we report a stochastic evaluation of the recently proposed LCC multireference perturbation theory [Sharma S., and Alavi A., J. Chem. Phys. 143, 102815, (2015)]. In this method both the zeroth order and first order wavefunctions are sampled stochastically by propagating simultaneously two populations of signed walkers. The sampling of the zeroth order wavefunction follows a set of stochastic processes identical to the one used in the FCIQMC method. To sample the first order wavefunction, the usual FCIQMC algorithm is augmented with a source term that spawns walkers in the sampled first order wavefunction from the zeroth order wavefunction. The second order energy is also computed stochastically but requires no additional overhead outside of the added cost of sampling the first order wavefunction. This fully stochastic method opens up the possibility of simultaneously treating large active spaces to account for static correlation and recovering the dynamical correlation using perturbation theory. This method is used to study a few benchmark systems including the carbon dimer and aromatic molecules. We have computed the singlet-triplet gaps of benzene and m-xylylene. For m-xylylene, which has proved difficult for standard CASSCF+PT, we find the singlet-triplet gap to be in good agreement with the experimental values.

physics.chem-ph↗

arXiv2016

Combining internally contracted states and matrix product states to perform multireference perturbation theory

We present two efficient and intruder-free methods for treating dynamic correlation on top of general multi-configuration reference wave functions---including such as obtained by the density matrix renormalization group (DMRG) with large active spaces. The new methods are the second order variant of the recently proposed multi-reference linearized coupled cluster method (MRLCC) [S. Sharma, A. Alavi, J. Chem. Phys. 143, 102815 (2015)], and of N-electron valence perturbation theory (NEVPT2), with expected accuracies similar to MRCI+Q and (at least) CASPT2, respectively. Great efficiency gains are realized by representing the first-order wave function with a combination of internal contraction (IC) and matrix product state perturbation theory (MPSPT). With this combination, only third order reduced density matrices (RDMs) are required. Thus, we obviate the need for calculating (or estimating) RDMs of fourth or higher order; these had so far posed a severe bottleneck for dynamic correlation treatments involving the large active spaces accessible to DMRG. Using several benchmark systems, including first and second row containing small molecules, Cr$_2$, pentacene and oxo-Mn(Salen), we shown that active spaces containing at least 30 orbitals can be treated using this method. On a single node, MRLCC2 and NEVPT2 calculations can be performed with over 550 and 1100 virtual orbitals, respectively. We also critically examine the errors incurred due to the three sources of errors introduced in the present implementation - calculating second order instead of third order energy corrections, use of internal contraction and approximations made in the reference wavefunction due to DMRG.

physics.chem-ph↗

arXiv2016

Edge Detection Based Shape Identification

Image recognition is the need of the hour. In order to be able to recognize an image, it is of immense importance that the image should be distinguishable from the background. In the present work, an approach is presented for automatic detection and recognition of regular 2D shapes in low noise environments. The work has a large number of direct applications in the real world. The algorithm proposed is based on locating the edges and thus, in turn calculating the area of the object helps in identification of a specified shape. The results were simulated using MATLAB tool are encouraging and validate the proposed algorithm. Index Terms: Edge Detection, Area Calculation, Shape Detection, Object Recognition

cs.CV↗

arXiv2016

Lossy Data Compression Using Logarithm

Lossy compression algorithms take advantage of the inherent limitations of the human eye and discard information that cannot be seen. In the present paper, a technique termed as Lossy Data Compression using Logarithm (LDCL) is proposed to compress incoming binary data in the form of a resultant matrix containing the logarithmic values of different chosen numeric sets. The proposed method is able to achieve compression ratio up to 60 in many major cases. Keywords: LDCL, Lossy Data Compression, Binary Reduction, Logarithmic Approach

cs.IT↗

arXiv2016

Cryptompress: A Symmetric Cryptography algorithm to deny Bruteforce Attack

Cryptompress, a new 128-bit (initial) private-key cryptography algorithm is proposed. It uses a block size of at least 30 bits and increments prior key size to additional 32 bits on each unsuccessful attempt of any means, including bruteforcing, further changing a specific portion of the cyphertext using the reformed Feistel network. Encryption process results from a proposed compression sequence developed using lookup table and shift operations followed by key generation. Eventually, four matrixes named add-sub matrix, reduced matrix, sequence matrix and term matrix are obtained which ultimately forms a cyphertext.

cs.CR↗

arXiv2015

Multireference linearized Coupled Cluster theory for strongly correlated systems using Matrix Product States

We propose a multireference linearized coupled cluster theory using matrix product states (MPS-LCC) which provides remarkably accurate ground-state energies, at a computational cost that has the same scaling as multireference configuration interaction singles and doubles (MRCISD), for a wide variety of electronic Hamiltonians. These range from first-row dimers at equilibrium and stretched geometries, to highly multireference systems such as the chromium dimer and lattice models such as periodic two-dimensional 1-band and 3-band Hubbard models. The MPS-LCC theory shows a speed up of several orders of magnitude over the usual DMRG algorithm while delivering energies in excellent agreement with converged DMRG calculations. Also, in all the benchmark calculations presented here MPS-LCC outperformed the commonly used multi-reference quantum chemistry methods in some cases giving energies in excess of an order of magnitude more accurate. As a size-extensive method that can treat large active spaces, MPS-LCC opens up the use of multireference quantum chemical techniques in strongly-correlated \emph{ab-initio} Hamiltonians, including two and three-dimensional solids.

physics.chem-ph↗

arXiv2014

Near exact excited states of the carbon dimer in a quadruple-zeta basis using a general non-Abelian density matrix renormalization group algorithm

We extend our previous work [J. Chem. Phys, \textbf{136}, 124121], which described a spin-adapted (SU(2) symmetry) density matrix renormalization group (DMRG) algorithm, to additionally utilize general non-Abelian point group symmetries. A key strength of the present formulation is that the requisite tensor operators are not hard-coded for each symmetry group, but are instead generated on the fly using the appropriate Clebsch-Gordan coefficients. This allows our single implementation to easily enable (or disable) any non-Abelian point group symmetry (including SU(2) spin symmetry). We use our implementation to compute the ground state potential energy curve of the C$_2$ dimer in the cc-pVQZ basis set (with a frozen-core), corresponding to a Hilbert space dimension of 10$^{12}$ many-body states. While our calculated energy lies within the 0.3 mE$_h$ error bound of previous initiator full configuration interaction quantum Monte Carlo (i-FCIQMC) and correlation energy extrapolation by intrinsic scaling (CEEIS) calculations, our estimated residual error is only 0.01 mE$_h$, much more accurate than these previous estimates. Further, due to the additional efficiency afforded by the algorithm, we compute the potential energy curves of twelve states: the three lowest levels for each of the irreducible representations $^1Σ^+_g$, $^1Σ^+_u$, $^1Σ^-_g$ and $^1Σ^-_u$, to an estimated accuracy within 0.1 mE$_h$ of the exact result in this basis.

physics.chem-ph↗

arXiv2014

Low-energy spectrum of iron-sulfur clusters directly from many-particle quantum mechanics

FeS clusters are a universal biological motif. They carry out electron transfer, redox chemistry, and even oxygen sensing, in diverse processes including nitrogen fixation, respiration, and photosynthesis. The low-lying electronic states are key to their remarkable reactivity, but cannot be directly observed. Here we present the first ever quantum calculation of the electronic levels of [2Fe-2S] and [4Fe-4S] clusters free from any model assumptions. Our results highlight limitations of long-standing models of their electronic structure. In particular, we demonstrate that the widely used Heisenberg-Double-Exchange model underestimates the number of states by 1-2 orders of magnitude, which can conclusively be traced to the absence of Fe d$\rightarrow$d excitations, thought to be important in these clusters. Further, the electronic energy levels of even the same spin are dense on the scale of vibrational fluctuations, and this provides a natural explanation for the ubiquity of these clusters in nature for catalyzing reactions.

physics.chem-ph↗

arXiv2014

A spin-adapted Density Matrix Renormalization Group algorithm for quantum chemistry

We extend the spin-adapted density matrix renormalization group (DMRG) algorithm of McCulloch and Gulacsi [Europhys. Lett.57, 852 (2002)] to quantum chemical Hamiltonians. This involves two key modifications to the non-spin-adapted DMRG algorithm: the use of a quasi-density matrix to ensure that the renormalised DMRG states are eigenvalues of $S^2$ , and the use of the Wigner-Eckart theorem to greatly reduce the overall storage and computational cost. We argue that the advantages of the spin-adapted DMRG algorithm are greatest for low spin states. Consequently, we also implement the singlet-embedding strategy of Nishino et al [Phys. Rev. E61, 3199 (2000)] which allows us to target high spin states as a component of a mixed system which is overall held in a singlet state. We evaluate our algorithm on benchmark calculations on the Fe$_2$S$_2$ and Cr$_2$ transition metal systems. By calculating the full spin ladder of Fe$_2$S$_2$ , we show that the spin-adapted DMRG algorithm can target very closely spaced spin states. In addition, our calculations of Cr$_2$ demonstrate that the spin-adapted algorithm requires only roughly half the number of renormalised DMRG states as the non-spin-adapted algorithm to obtain the same accuracy in the energy, thus yielding up to an order of magnitude increase in computational efficiency.

physics.chem-ph↗

arXiv2014

Spectroscopic accuracy directly from quantum chemistry: application to ground and excited states of beryllium dimer

We combine explicit correlation via the canonical transcorrelation approach with the density matrix renormalization group and initiator full configuration interaction quantum Monte Carlo methods to compute a near-exact beryllium dimer curve, {\it without} the use of composite methods. In particular, our direct density matrix renormalization group calculations produce a well-depth of $D_e$=931.2 cm$^{-1}$ which agrees very well with recent experimentally derived estimates $D_e$=929.7$\pm 2$~cm$^{-1}$ [Science, 324, 1548 (2009)] and $D_e$=934.6~cm$^{-1}$ [Science, 326, 1382 (2009)]], as well the best composite theoretical estimates, $D_e$=938$\pm 15$~cm$^{-1}$ [J. Phys. Chem. A, 111, 12822 (2007)] and $D_e$=935.1$\pm 10$~cm$^{-1}$ [Phys. Chem. Chem. Phys., 13, 20311 (2011)]. Our results suggest possible inaccuracies in the functional form of the potential used at shorter bond lengths to fit the experimental data [Science, 324, 1548 (2009)]. With the density matrix renormalization group we also compute near-exact vertical excitation energies at the equilibrium geometry. These provide non-trivial benchmarks for quantum chemical methods for excited states, and illustrate the surprisingly large error that remains for 1$^1Σ^-_g$ state with approximate multi-reference configuration interaction and equation-of-motion coupled cluster methods. Overall, we demonstrate that explicitly correlated density matrix renormalization group and initiator full configuration interaction quantum Monte Carlo methods allow us to fully converge to the basis set and correlation limit of the non-relativistic Schrödinger equation in small molecules.

physics.chem-ph↗

arXiv2014

A flexible multi-reference perturbation theory by minimizing the Hylleraas functional with matrix product states

We describe a formulation of multi-reference perturbation theory that obtains a rigorous upper bound to the second order energy by minimizing the Hylleraas functional in the space of matrix product states (MPS). The first order wavefunctions so obtained can also be used to compute the third order energy with little overhead. Our formulation has several advantages including (i) flexibility with respect to the choice of zeroth order Hamiltonian, (ii) recovery of the exact uncontracted multi-reference perturbation theory energies in the limit of large MPS bond dimension, (iii) no requirement to compute high body density matrices, (iv) an embarrassingly parallel algorithm (scaling up to the number of virtual orbitals, squared, processors). Preliminary numerical examples show that the MPS bond dimension required for accurate first order wavefunctions scales sub-linearly with the size of the basis.

physics.chem-ph↗

arXiv2014

Subluminal light pulse propagation in a Λ-type atom-molecule coupled system

We show theoretically the presence of electromagnetically induced transparency (EIT) like feature in a Λ-type atom-molecule coupled system. We demonstrate that EIT in such a systems has a sharp dispersion characteristic which is useful to slow down light propagation in a medium. The results of our model calculations show that, it is possible to achieve a time delay of the order of 1 ms for a probe field propagating a distance of 1 cm through a medium of ultracold diatomic molecules coupled to the continuum of atom-atom collisional states with a control field. This enables one to reduce the group velocity of the light much below 100 m/s with more than 25% transmission.

physics.optics↗

arXiv2014

The intermediate and spin-liquid phase of the half-filled honeycomb Hubbard model

We obtain the phase-diagram of the half-filled honeycomb Hubbard model with density matrix embedding theory, to address recent controversy at intermediate couplings. We use clusters from 2-12 sites and lattices at the thermodynamic limit. We identify a paramagnetic insulating state, with possible hexagonal cluster order, competitive with the antiferromagnetic phase at intermediate coupling. However, its stability is strongly cluster and lattice size dependent, explaining controver- sies in earlier work. Our results support the paramagnetic insulator as being a metastable, rather than a true, intermediate phase, in the thermodynamic limit.

cond-mat.str-el↗