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Amlan K. Roy

Publications and source records attributed to Amlan K. Roy.

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Density functional studies on the hollow resonances in Li-isoelectronic sequence (Z=4--10

In this sequel to our work on triply excited hollow resonances in three-electron atomic systems, a density functional theory (DFT)-based formalism is employed to investigate similar resonances in Li-isoelectronic series (Z=4--10). A combination of the work-function-based local nonvariational exchange potential and the popular gradient plus Laplacian included Lee-Yang-Parr correlation energy functional is used. First, all the 8 n=2 intrashell states of B$^{2+}$, N$^{4+}$ and F$^{6+}$ are presented, which are relatively less studied in the literature compared to the remaining 4 members. Then calculations are performed for the 8 $2l2l'$n$l"$ (3$\leq$n$\leq$6) hollow resonance series; {\em viz.,} 2s$^2$ns $^2$S$^e$, 2s$^2$np $^2$P$^o$, 2s$^2$nd $^2$D$^e$, 2s2pns $^4$P$^o$, 2s2pnp $^4$D$^e$, 2p$^2$ns $^4$P$^e$, 2p$^2$np $^4$D$^o$ and 2p$^2$ns $^2$D$^e$, of all the 7 positive ions. Next, as an illustration, higher resonance positions of the 2s$^2$ns $^2$S$^e$ series are calculated for all the ions with a maximum of n=25. The excitation energies calculated from this single-determinantal approach are in excellent agreement with the available literature data (for the n=2 intrashell states the deviation is within 0.125% and excepting only one case, the same for the resonance series is well below 0.50%). With an increase in Z, the deviations tend to decrease. Radial densities are also presented for some of the selected states. The only result available in the literature for the lower resonances (corresponding to a maximum of n=17) have been reported very recently. The n$>$16 ($>17$ for F$^{6+}$) resonances are examined here for the first time. This gives a promising viable and general DFT scheme for the accurate calculation of these and other hollow resonances in many-electron atoms.

physics.atom-ph↗

Studies on the hollow states of atomic lithium by a density functional approach

Density functional calculations are performed for twelve $2l2l'$n$l"$ (n$\geq$2) triply excited hollow resonance series of Li, {\em viz.,} 2s$^2$ns $^2$S$^e$, 2s$^2$np $^2$P$^o$, 2s$^2$nd $^2$D$^e$, 2p$^2$ns $^2$D$^e$,$^4$P$^e$, 2s2pns $^4$P$^o$, 2s2pnp $^4$D$^e$, 2p$^2$np $^2$F$^o$,$^4$D$^o$, 2p$^2$nd $^2$G$^e$, $^4$F$^e$ and 2s2pnd $^4$F$^o$, covering a total of about 270 low-, moderately high- and high-lying states, with n as high as up to 25. The work-function-based exchange potential and the nonlinear gradient plus Laplacian included Lee-Yang-Parr correlation energy functional is used. The relevant Kohn-Sham-type equation is solved numerically using the generalized pseudospectral method offering nonuniform, optimal spatial discretization to obtain the orbitals and densities. Except for the one state, the discrepancy in the calculated state energies remains well within 0.98%, whereas the excitation energies deviate by 0.02--0.58% compared to the available experimental and other theoretical results. Additionally companion calculations are also presented for the 37 $3l3l'$n$l"$ (n$\geq$3) doubly hollow states (seven are n=3 intrashell type) of Li with both K and L shells empty (up to n=6) in the photon energy range 175.63--180.51 eV, with varying symmetries and multiplicities. Our calculation shows good agreement with the recent literature data for the only two such doubly hollow states reported so far, {\em viz.,} 3s$^2$3p $^2$P$^o$ and 3s3p$^2$ $^4$P$^e$. The resonance series are found to be inextricably entangled to each other, leading to complicated behavior in their positions. Many new states are reported here for the first time. This provides a simple, efficient and general scheme for the accurate calculation of these and other multiply excited Rydberg series of many-electron atomic systems within density functional theory.

physics.chem-ph↗

Calculation of the bound states of power-law and logarithmic potentials through a generalized pseudospectral method

Bound states of the power-law and logarithmic potentials are calculated using a generalized pseudospectral method. The solution of the single-particle Schrödinger equation in a nonuniform and optimal spatial discretization offers accurate eigenvalues, densities and expectation values. The calculations are carried out for states with arbitrary $n$ and $\ell$ quantum numbers. Comparisons are made with the available literature data and excellent agreement is observed. In all the cases, the present method yields considerably improved results over the other existing calculations. Some new states are reported.

quant-ph↗

Calculation of the spiked harmonic oscillators through a generalized pseudospectral method

The generalized pseudospectral method is employed for the accurate calculation of eigenvalues, densities and expectation values for the spiked harmonic oscillators. This allows \emph{nonuniform} and \emph{optimal} spatial discretization of the corresponding single-particle radial Schrödinger equation satisfying the Dirichlet boundary conditions leading to the standard diagonalization of the symmetric matrices. The present results for a large range of potential parameters are in excellent agreement with those from the other accurate methods available in the literature. The ground and excited states (both low as well as high angular momentum states) are obtained with equal ease and accuracy. Some new states including the higher excited states are reported here for the first time. This offers a simple, accurate and efficient method for the treatment of these and a wide variety of other singular potentials of physical and chemical interest in quantum mechanics.

quant-ph↗

Studies on some exponential-screened Coulomb potentials

The generalized pseudospectral method is employed to study the bound-state spectra of some of the exponentially screened Coulomb potentials, \emph{viz.}, the exponential cosine screened Coulomb (ECSC) and general exponential screened Coulomb (GESC) potential, with special emphasis on \emph{higher} states and \emph{stronger} interaction. Eigenvalues accurate up to eleven significant figures are obtained through a non-uniform optimal spatial discretization of the radial Schrödinger equation. All the 55 eigenstates of ECSC potential with $n \le 10$ and 36 eigenstates of GESC potential with $n \le 8$ are considered for arbitrary values of the screening parameter, covering a wide range of interaction. Excited states as high as up to $n=18$ have been computed with high accuracy for the first time. Excellent agreement with the literature data has been observed in all cases. All the GESC eigenstates are calculated with much greater accuracy than the existing methods available in literature. Many $l \ne 0$ states of this potential are reported here. In both cases, a detailed variation of energies with respect to the parameters in potential is monitored.

quant-ph↗

Bound state spectra of the 3D rational potential

We present bound state spectra of the 3D rational potential, $V(r)=r^2 + λr^2/(1+gr^2)$, $g>0$, by means of the generalized pseudospectral method. All the thirty states corresponding to $n$=0--9 are considered for the first time for a broad range of coupling parameters. These results surpass the accuracy of \emph{all} other existing calculations published so far except the finite-difference method, which yields similar accuracy as ours. Variation of energies and radial distribution functions is followed with respect to the interaction parameters. Special emphasis has been laid on \emph{higher} excitations and \emph{negative} values of the interaction, where relatively less work has been reported. The energy sequence is found to be different for positive and negative interaction; numerically following a mirror-image relationship \emph{usually}, if not always. Additionally, twenty energy splittings arising from certain levels belonging to $n$=0--9 are systematically studied as functions of the potential parameters. Several new states (including the higher ones) are presented.

quant-ph↗

Pseudopotential density functional treament of atoms and molecules in cartesian coordinate grid

This is a follow-up of our recently proposed work on pseudopotential calculation (Ref. [21]) of atoms and molecules within DFT framework, using cartesian coordinate grid. Detailed results are presented to demonstrate the usefulness, applicability of the same for a larger set of species (5 atoms; 53 molecules) and exchange-correlation functionals (local, nonlocal). A thorough comparison on total, component, ionization, atomization energies, eigenvalues, potential energy curves with available literature data shows excellent agreement. Additionally, HOMO energies for a series of molecules show significant improvements by using the Leeuwen-Baerends exchange potential, compared to other functionals considered. Comparison with experiments has been made, wherever possible.

physics.chem-ph↗

Ground and excited states of Li$^-$, Be$^-$ through a density-based approach

Density functional calculations are performed for ground [He]2s$^2$ $^1$S$^e$, and three metastable bound excited states, 1s2s2p$^2$ $^5$P$^e$, 1s2p$^3$ $^5$S$^o$, 1s2s2p3p $^5$P$^e$ of Li$^-$ and [He]2s2p$^2$ $^4$P$^e$, [He]2p$^3$ $^4$S$^o$, 1s2s2p$^3$ $^6$S$^o$ of Be$^-$ each. The work-function-based exchange potential is used, while the correlation effects are included by employing the Lee-Yang-Parr potential. The relevant nonrelativistic KS equation is solved by means of a generalized pseudospectral discretization scheme offering nonuniform and optimal spatial grid. Computed total energies, radial densities, selected density moments, as well as two transition wavelengths (1s2s2p$^2$ $^5$P$^e \to$1s2p$^3$ $^5$S$^o$ of Li$^-$, [He]2s2p$^2$ $^4$P$^e \to$ [He]2p$^3$ $^4$S$^o$ of Be$^-$) show reasonably good agreement with the available theoretical and experimental data. The term energies show an absolute deviation of 0.007--0.171% with the largest deviation being observed for the even-parity $^5$P state of Li$^-$. The transition wavelengths of Li$^-$, Be$^-$ are calculated within 0.891 and 0.438% of the experimental values. This offers a simple practical route towards accurate reliable calculation of excited states of anions within density functional theory.

physics.chem-ph↗

Density functional calculation of many-electron systems in cartesian coordinate grid

A recently developed density functional method, within Hohenberg-Kohn-Sham framework, is used for faithful description of atoms, molecules in Cartesian coordinate grid, by using an LCAO-MO ansatz. Classical Coulomb potential is obtained by means of a Fourier convolution technique. All two-body potentials (including exchange-correlation (XC)) are constructed directly on real grid, while their corresponding matrix elements are computed from numerical integration. Detailed systematic investigation is made for a representative set of atoms/molecules through a number of properties like total energies, component energies, ionization energies, orbital energies, etc. Two nonlocal XC functionals (FT97 and PBE) are considered for pseudopotential calculation of 35 species while preliminary all-electron results are reported for 6 atoms using the LDA XC density functional. Comparison with literature results, wherever possible, exhibits near-complete agreement. This offers a simple efficient route towards accurate reliable calculation of many-electron systems in the Cartesian grid. Future prospect of this method is also discussed.

physics.chem-ph↗

Spherically confined isotropic harmonic oscillator

The generalized pseudospectral Legendre method is used to carry out accurate calculations of eigenvalues of the spherically confined isotropic harmonic oscillator with impenetrable boundaries. The energy of the confined state is found to be equal to that of the unconfined state when the radius of confinement is suitably chosen as the location of the radial nodes in the unconfined state. This incidental degeneracy condition is numerically shown to be valid in general. Further, the full set of pairs of confined states defined by the quantum numbers [(n+1, \ell) ; (n, \ell+2)], n = 1,2,.., and with the radius of confinement {(2 \ell +3)/2}^{1/2} a.u., which represents the single node in the unconfined (1, \ell) state, is found to display a constant energy level separation exactly given by twice the oscillator frequency. The results of similar numerical studies on the confined Davidson oscillator with impenetrable boundary as well as the confined isotropic harmonic oscillator with finite potential barrier are also reported .The significance of the numerical results are discussed.

quant-ph↗