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M. C. Valsakumar

Publications and source records attributed to M. C. Valsakumar.

At least 19 recordsLinked to original sources
arXiv2016

Delineating the role of ripples on thermal expansion of honeycomb materials:graphene, 2D-h-BN and monolayer(ML)-MoS2

We delineated the role of thermally excited ripples on thermal expansion properties of 2D honeycomb materials (free-standing graphene, 2D h-BN, and ML-MoS2), by explicitly carrying out three-dimensional (3D) and two-dimensional (2D) molecular dynamics simulations. In 3D simulations, the in-plane lattice parameter (a-lattice) of graphene and 2D h-BN shows thermal contraction over a wide range of temperatures and exhibits a strong system size dependence. The 2D simulations of the very same system show a reverse trend, where the a-lattice is expanding in the whole computed temperature range. Contrary to graphene and 2D h-BN, the a-lattice of ML-MoS2 shows thermal expansion in both 2D and 3D simulations and their system size dependence is marginal. By analyzing the phonon dispersion at 300 K, we found that the discrepancy between 2D and 3D simulations of graphene and 2D h-BN is due to the absence of out-of-plane bending mode (ZA) in 2D simulations, which is responsible for thermal contraction of a-lattice at low temperature. Meanwhile, all the phonon modes are present in 2D phonon dispersion of ML-MoS2, which indicates that the origin of ZA mode is not purely due to out-of-plane movement of atoms and also its effect on thermal expansion is not significant as found in graphene and 2D h-BN

cond-mat.mtrl-sci↗
arXiv2015

Phase stability and lattice dynamics of ammonium azide under hydrostatic compression

We have investigated the effect of hydrostatic pressure and temperature on phase stability of hydro-nitrogen solids using dispersion corrected Density Functional Theory calculations. From our total energy calculations, Ammonium Azide (AA) is found to be the thermodynamic ground state of N$_4$H$_4$ compounds in preference to Trans-Tetrazene (TTZ), Hydro-Nitrogen Solid-1 (HNS-1) and HNS-2 phases. We have carried out a detailed study on structure and lattice dynamics of the equilibrium phase (AA). AA undergoes a phase transition to TTZ at around $\sim$ 39-43 GPa followed by TTZ to HNS-1 at around 80-90 GPa under the studied temperature range of 0-650 K. The accelerated and decelerated compression of $a$ and $c$ lattice constants suggest that the ambient phase of AA transforms to a tetragonal phase and then to a low symmetry structure with less anisotropy up on further compression. We have noticed that the angle made by Type-II azides with $c$-axis shows a rapid decrease and reaches a minimum value at 12 GPa, and thereafter increases up to 50 GPa. Softening of the shear elastic moduli is suggestive of a mechanical instability of AA under high pressure. In addition, we have also performed density functional perturbation theory calculations to obtain the vibrational spectrum of AA at ambient as well as at high pressures. Further, we have made a complete assignment of all the vibrational modes which is in good agreement with the experimental observations at ambient pressure. Also the calculated pressure dependent IR spectra show that the N-H stretching frequencies undergo a red and blue-shift corresponding to strengthening and weakening of hydrogen bonding, respectively below and above 4 GPa.

cond-mat.mtrl-sci↗
arXiv2014

High Pressure Structural Stability, and Optical Properties of Scheelite type ZrGeO$_4$ and HfGeO$_4$ X-ray Phosphor Hosts

\emph{Ab-initio} calculations were performed on the scheelite type MGeO$_4$ (M = Hf, and Zr) compounds which find wide range of applications such as in x-ray imaging. We have studied the high pressure structural stability, elastic constants, electronic structure and optical properties of these compounds through density functional theory calculations. Two different density functional approaches namely plane wave pseudopotential method (PW-PP) and full potential linearized augmented plane wave method (FP-LAPW) were used for the present study. The ground state structural and vibrational properties are calculated and found to be in good agreement with experimental data. The compressibility of Zr and Hf germanates is found to be anisotropic as the a-axis is less compressible over c-axis due to the presence of Ge-O bonds along a-axis which is further confirmed from the ordering of the elastic constants that follows C$_{11}$ $>$ C$_{33}$. The electronic structure of the compounds has been calculated through recently developed Tran Blaha-modified Becke Johnson potential. The calculated electronic structure shows that the compounds are insulators with a gap of 5.39 eV for ZrGeO$_4$ and 6.25 eV for HfGeO$_4$ respectively. Optical anisotropy of these compounds are revealed from the computed optical properties such as complex dielectric function, refractive index, and absorption coefficient. In addition, it is observed that Ti doped ZrGeO$_4$ and HfGeO$_4$ turns out to be a good phosphor as the pristine compounds have the energy gap greater than the visible range upon Ti doping bandgap reduces as a result emission spectra occurs in the visible region and is well explained in the present study.

cond-mat.mtrl-sci↗
arXiv2014

Thermoelectric properties of marcasite and pyrite FeX$_2$(X=Se,Te): A first principle study

Electronic structure and thermoelectric properties of marcasite (m) and synthetic pyrite (p) phases of FeX$_2$ (X=Se,Te) have been investigated using first principles density functional theory and Boltzmann transport equation. The plane wave pseudopotential approximation was used to study the structural properties and full-potential linear augmented plane wave method was used to obtain the electronic structure and thermoelectric properties (thermopower and power factor scaled by relaxation time). From total energy calculations we find that m-FeSe$_2$ and m-FeTe$_2$ are stable at ambient conditions and no structural transition from marcasite to pyrite is seen under the application of hydrostatic pressure. The calculated ground state structural properties agree quite well with available experiments. From the calculated thermoelectric properties, we find that both m and p forms are good candidates for thermoelectric applications. However, hole doped m-FeSe$_2$ appears to be the best among all the four systems.

cond-mat.mtrl-sci↗
arXiv2013

Phase Stability and Thermoelectric Properties of the Mineral FeS2: An Ab Initio Study

First principles calculations were carried out to study the phase stability and thermoelectric properties of the naturally occurring marcasite phase of FeS$_2$ at ambient condition as well as under pressure. Two distinct density functional approaches has been used to investigate the above mentioned properties. The plane wave pseudopotential approach was used to study the phase stability and structural, elastic, and vibrational properties. The full potential linear augment plane wave method has been used to study the electronic structure and thermoelectric properties. From the total energy calculations, it is clearly seen that marcasite FeS$_2$ is stable at ambient conditions, and it undergoes a first order phase transition to pyrite FeS$_2$ at around 3.7 GPa with a volume collapse of about 3$\%$. The calculated ground state properties such as lattice parameters, bond lengths and bulk modulus of marcasite FeS$_2$ agree quite well with the experiment. Apart from the above studies, phonon dispersion curves unambiguously indicate that marcasite phase is stable under ambient conditions. Further, we do not observe any phonon softening across the marcasite to pyrite transition and the possible reason driving the transition is also analyzed in the present study, which has not been attempted earlier. In addition, we have also calculated the electronic structure and thermoelectric properties of the both marcasite and pyrite FeS$_2$. We find a high thermopower for both the phases, especially with p-type doping, which enables us to predict that FeS$_2$ might find promising applications as good thermoelectric materials.

cond-mat.mtrl-sci↗
arXiv2011

Incorporation of surface correction and anharmonic correction to vacancy formation energy for nickel and copper: bridging the gap between Density Functional Theory and experiment

Density functional theory (DFT) has been used to estimate vacancy formation enthalpy (H_fv) for a few transition metals like nickel (Ni) and copper (Cu). It is shown that, for these metals, H_fv is underestimated considerably by DFT. The aim of the present work is to bridge the gap between the estimates made by DFT calculations and experiments. The sources of this discrepancy are identified as to be related to the opening up of the surface like region surrounding the vacancy, and the temperature induced anharmonic contribution. The surface related correction to H_fv has been estimated by a jellium based model originally proposed by Mattsson et al. [Phys. Rev. B 73 (2006) 195123] and subsequently modified by Nandi et al. [J. Phys.:Cond. Matt. 22 (2010) 345501]. In this paper, we have estimated the temperature induced anharmonic contribution to H_fv using density functional perturbation theory. Finally, it is shown that incorporation of both the surface correction and anharmonic correction to H_fv, results in a better agreement with the experimental data.

cond-mat.mtrl-sci↗
arXiv2011

Efficacy of surface error corrections to density functional theory calculations of vacancy formation energy in transition metals

We calculate properties like equilibrium lattice parameter, bulk modulus and monovacancy formation energy for nickel (Ni), iron (Fe) and chromium (Cr) using Kohn-Sham density functional theory (DFT). We compare relative performance of local density approximation (LDA) and generalized gradient approximation (GGA) for predicting such physical properties for these metals. We also make a relative study between two different flavors of GGA exchange correlation functional, namely, PW91 and PBE. These calculations show that there is a discrepancy between DFT calculations and experimental data. In order to understand this discrepancy in the calculation of vacancy formation energy, we introduce a correction for the surface intrinsic error corresponding to an exchange correlation functional using the scheme implemented by Mattsson et al. [Phys. Rev. B 73, 195123 (2006)] and compare the effectiveness of the correction scheme for Al and the 3d-transition metals.

cond-mat.mtrl-sci↗
arXiv2010

Generalization of the detailed fluctuation theorem for Non-Hamiltonian Dynamics

Detailed fluctuation theorem, a microscopic version of the steady state fluctuation theorem, has been proposed by Jarzynski and demonstrated in the case of Hamiltonian systems weakly coupled with reservoirs. We show that an identical theorem for phase space compressibility rate can be derived for systems evolving under non-Hamiltonian extended system dynamics, without certain limiting assumptions made in the original work. Our derivation is based on the non-Hamiltonian phase space formulation of statistical mechanics and does not rely on any assumptions of thermodynamic nature. This version of the detailed fluctuation theorem is shown to be generic enough to be applicable to several thermostatting schemes. It is shown that in equilibrium, this detailed fluctuation theorem boils down to the detailed balance equation and it is further shown to reproduce the Jarzynski's work theorem for driven systems.

cond-mat.stat-mech↗
arXiv2007

Bound Pairs: Direct Evidence for Long-range Attraction between Like-Charged Colloids

We report observations of stable bound pairs in very dilute deionized aqueous suspensions of highly charged polystyrene colloidal particles, with monovalent counterions, using a confocal laser scanning microscope. Through an analysis of several thousands of time series of confocal images recorded deep inside the bulk suspension, we find that the measured pair-potential, U(r) has a long-range attractive component with well depths larger than the thermal energy. These observations provide a direct and unequivocal evidence for the existence of long-range attraction in U(r) of like-charged colloidal particles.

cond-mat.soft↗
arXiv2007

Ferromagnetism in cobalt doped n-GaN

Ferromagnetic ordering is reported in the post-annealed samples of Co doped n-GaN formed by Co+ implantation. A maximum Curie temperature ~ 250K is recorded for the sample with 8 atomic percent Co. Particle induced x-ray emission-channeling study confirmed the substitutional Co in Ga lattice site. Local atomic arrangement around magnetic impurities is also analyzed using Raman study. A disordered model with carrier mediated coupling of localized magnetic moments is made responsible for the observed ferromagnetic ordering.

cond-mat.mtrl-sci↗
arXiv2007

Soft modes and NTE in Zn(CN)2 from Raman spectroscopy and first principles calculations

We have studied Zn(CN)2 at high pressure using Raman spectroscopy, and report Gruneisen parameters of the soft phonons. The phonon frequencies and eigen vectors obtained from ab-initio calculations are used for the assignment of the observed phonon spectra. Out of the eleven zone-centre optical modes, six modes exhibit negative Gruneisen parameter. The calculations suggest that the soft phonons correspond to the librational and translational modes of CN rigid unit, with librational modes contributing more to thermal expansion. A rapid disordering of the lattice is found above 1.6 GPa from X-ray diffraction.

cond-mat.mtrl-sci↗
arXiv2005

Stochasticity, decoherence and an arrow of time from the discretization of time?

Certain intriguing consequences of the discreteness of time on the time evolution of dynamical systems are discussed. In the discrete-time classical mechanics proposed here, there is an {\it arrow of time} that follows from the fact that the replacement of the time derivative by the backward difference operator alone can preserve the non-negativity of the phase space density. It is seen that, even for free particles, all the degrees of freedom are {\it correlated} in principle. The forward evolution of functions of phase space variables by a finite number of time steps, in this discrete-time mechanics, depends on the entire continuous-time history in the interval $[0, \infty]$. In this sense, discrete time evolution is {\it nonlocal} in time from a continuous-time point of view. A corresponding quantum mechanical treatment is possible {\it via} the density matrix approach. The interference between non-degenerate quantum mechanical states decays exponentially. This {\it decoherence} is present, in principle, for all systems; however, it is of practical importance only in macroscopic systems, or in processes involving large energy changes.

quant-ph↗
arXiv2005

Electronic structure of Li2Pd3B and Li2Pt3B

Li2Pd3B is known to be superconducting, while the isotypical Li2Pt3B compound is not. Electronic structures of Li2Pd3B and Li2Pt3B have been calculated in order to obtain an insight into this surprising difference, through an analysis of the differences in the band structures. The electronic structures of these systems were obtained using the Full Potential Linear Augmented Plane Wave plus local orbitals (FP-LAPW+lo) method and it was found that four bands cross the Fermi level (EF). Out of these four bands, only two bands contribute significantly to the density of states at the EF. One of these bands is a hole band and the other an electron band. Thus at least a two-band model is required for studying the electronic properties of the Pd and Pt compounds. These two bands are rather narrow and hence the coulombic correlations effects can be significant.

cond-mat.supr-con↗
arXiv2004

Structural Behavior of Non-Oxide Perovskite Superconductor MgCNi$_{3}$ at Pressures up to 32 GPa

We report the pressure dependence of the structural parameters of the non-oxide perovskite superconductor MgCNi$_{3}$ up to 32 GPa using a diamond anvil cell and synchrotron x-rays at room temperature. The structure of the compound remains in the Pm-3m cubic symmetry throughout the pressure range. The bulk modulus $B_{0}=156.9\pm0.2$GPa with $B_{0}^{\prime}=9.8$obtained by fitting the pressure-volume data is in good agreement with theoretical calculations reported earlier. An anomalous shift of the (111) and (200) lines observed above 9 GPa indicates a possible local short range distortion that is consistent with earlier studies.

cond-mat.supr-con↗
arXiv2004

Stability of differential equations associated with a class of one dimensional maps

Discrete time evolution of one-dimensional maps is embedded in continuous time by truncating the Taylor series expansion of the time evolution operator to a finite order N. Truncations with N > 4 leads to unconditional instability. Generalization of the truncated models with N = 3 and 4 shows dynamical behaviour characteristic of systems with a riddled parameter space.

math-ph↗
arXiv2003

Tuning of the superconducting and ferromagnetic transitions by Cu doping for Ru in GdSr2RuCu2O8

In order to explore the possibility of tuning superconducting and ferromagnetic transitions by Cu doping (for Ru) in GdSr2RuCu2O8, we have carried out synthesis and characterization of GdSr2Ru{1-x}Cu{2+x)O8 (x = 0, 0.05, 0.1, 0.2) and studied their physical properties. Coexistence of superconductivity and ferromagnetism is observed in all the Cu doped samples studied here. The zero field susceptibility data suggests formation of a spontaneous vortex phase. Cu doping decreases the ferromagnetic Curie temperature, whereas the superconducting transition temperature increases until an optimal concentration x~0.1. This reflects an increase in hole transfer to the CuO2 planes and reduction of ferromagnetic order within the ruthenate layers.

cond-mat.supr-con↗
arXiv2002

Study of Normal and Superconducting States of MgCNi_3 upon Fe and Co Substitution and External Pressure

Results of our study on the superconducting and normal state properties of the recently discovered superconductor MgCNi_3, the effect of Fe and Co substitution at the Ni site and the effect of pressure are reported. It is shown that a two band model provides a consistent interpretation of the temperature dependence of the normal state resistance and the Hall constant. Whereas band structure calculations suggest an increase in T_c upon partial substitution of Ni with Fe and Co, Co substitution quenches superconductivity and Fe substitution leads to an increase followed by a decrease in T_c. The observed variation of T_c may be explained in terms of a competition between increase in T_c due to increase in density of states and a decrease due to spin fluctuations. Based on these results, it is suggested that the spin fluctuations are weaker in Fe doped samples as compared to the Co doped ones. An initial decrease in T_c (and the normal state resistance) followed by an increase is observed on application of pressure. The decrease in T_c for small applied pressures can be understood in terms of the decrease in the density of states at the Fermi level. The subsequent increase in T_c with pressure is due to a lattice softening or a structural phase transition, consistent with the band structure calculations. It is conjectured that suppression of spin fluctuations by pressure may also be responsible for the observed increase in T_c at higher pressures.

cond-mat.supr-con↗