773 research outputs found
Rapid topography mapping of scalar fields: Large molecular clusters
The following article appeared in Journal of Chemical Physics 137.7 (2012): 074116 and may be found at http://scitation.aip.org/content/aip/journal/jcp/137/7/10.1063/1.4746243An efficient and rapid algorithm for topography mapping of scalar fields, molecular electron density (MED) and molecular electrostatic potential (MESP) is presented. The highlight of the work is the use of fast function evaluation by Deformed-atoms-in-molecules (DAM) method. The DAM method provides very rapid as well as sufficiently accurate function and gradient evaluation. For mapping the topography of large systems, the molecular tailoring approach (MTA) is invoked. This new code is tested out for mapping the MED and MESP critical points (CP's) of small systems. It is further applied to large molecular clusters viz. (H 2O) 25, (C 6H 6) 8 and also to a unit cell of valine crystal at MP26-31G(d) level of theory. The completeness of the topography is checked by extensive search as well as applying the Poincaré-Hopf relation. The results obtained show that the DAM method in combination with MTA provides a rapid and efficient route for mapping the topography of large molecular systemsAuthors thank the Center for Development of Advanced Computing (C-DAC), Pune for financial and computational support. S.R.G. is grateful to the Department of Science and Technology (DST) for the award of J. C. Bose National Fellowship. R. López acknowledges partial funding from the CAM (S2009_PPQ-1545, LIQUORGAS) and MICINN (CTQ2010-19232). Authors are also thankful to Dr. Graeme M. Day, University of Cambridge, for providing the coordinates of unit cell of valine crystal and to Dr. V. Subramanian, CLRI, Chennai for providing some test run
Complexity analysis of Klein-Gordon single-particle systems
The Fisher-Shannon complexity is used to quantitatively estimate the
contribution of relativistic effects to on the internal disorder of
Klein-Gordon single-particle Coulomb systems which is manifest in the rich
variety of three-dimensional geometries of its corresponding quantum-mechanical
probability density. It is observed that, contrary to the non-relativistic
case, the Fisher-Shannon complexity of these relativistic systems does depend
on the potential strength (nuclear charge). This is numerically illustrated for
pionic atoms. Moreover, its variation with the quantum numbers (n, l, m) is
analysed in various ground and excited states. It is found that the
relativistic effects enhance when n and/or l are decreasing.Comment: 4 pages, 3 figures, Accepted in EPL (Europhysics Letters
Universal trend of the information entropy of a fermion in a mean field
We calculate the information entropy of single-particle states in
position-space and momentum-space for a nucleon in a nucleus, a
particle in a hypernucleus and an electron in an atomic cluster. It
is seen that and obey the same approximate functional form as
functions of the number of particles, ({\rm or}
in all of the above many-body systems in position- and momentum- space
separately. The net information content is a slowly varying
function of of the same form as above. The entropy sum is
invariant to uniform scaling of coordinates and a characteristic of the
single-particle states of a specific system. The order of single-particle
states according to is the same as their classification according to
energy keeping the quantum number constant. The spin-orbit splitting is
reproduced correctly. It is also seen that enhances with
excitation of a fermion in a quantum-mechanical system. Finally, we establish a
relationship of with the energy of the corresponding single-particle
state i.e. . This relation holds for all the
systems under consideration.Comment: 9 pages, latex, 6 figure
Information entropy as a measure of the quality of a nuclear density distribution
The information entropy of a nuclear density distribution is calculated for a
number of nuclei. Various phenomenological models for the density distribution
using different geometry are employed. Nuclear densities calculated within
various microscopic mean field approaches are also employed. It turns out that
the entropy increases on going from crude phenomenological models to more
sophisticated (microscopic) ones. It is concluded that the larger the
information entropy, the better the quality of the nuclear density
distribution. An alternative approach is also examined: the net information
content i.e. the sum of information entropies in position and momentum space
. It is indicated that is a maximum, when the best
fit to experimental data of the density and momentum distributions is attained.Comment: 12 pages, LaTex, no figures, Int. J. of Mod. Phys. E in pres
Enabling rapid and accurate construction of CCSD(T)-level potential energy surface of large molecules using molecular tailoring approach
The construction of the potential energy surface (PES) of even a medium-sized
molecule employing correlated theory, such as CCSD(T), is an arduous task due
to the high computational cost. In this Letter, we report the possibility of
efficient construction of such a PES employing the molecular tailoring approach
(MTA) on off-the-shelf hardware. The full calculation (FC) as well as MTA
energies at CCSD(T)/aug-cc-pVTZ level for three test molecules, viz.
acetylacetone, N-methyacetamide, and tropolone are reported. All the MTA
energies are in excellent agreement with their FC counterparts (typical error
being sub-millihartree) with a time advantage factor of 3 to 5. The energy
barrier from the ground- to transition-state is accurately captured. Further,
the accuracy and efficiency of the MTA method for estimating energy gradients
at CCSD(T) level are demonstrated. This work brings out the possibility of the
construction of PES for large molecules using MTA with the computational
economy at a high level of theory and/or basis set
Co-operative electrostatics for understanding crown ether hydration patterns
A prototype problem in supramolecular chemistry is: Would it be possible to understand qualitative trends in hydration preocess of crown ether from simple considerations at the molecular levels? An answer is offered for the hydration of 18-crown-6 in terms of co-operative electrostatic effects. These effects are monitored by mapping the molecular electrostatic potential topography of 18-crown-6 as well as various interemediate hydrated species, followed by electrostatic modelling. All model calculations have been done at ab-initio HF/6-31G** level. The trends of these hydration patterns are in good agreement with the corresponding fully optimized ab-initio ones. Final structure of 18C6·4H2O is quite similar to the corresponding experimental crystal structure. Such an electrostatics-based method seems to be an excellent general tool for understanding weak interactions in supramolecular chemistry
Electron momentum distributions and compton profiles of some molecules with FSGO model
The electron momentum distributions and the Compton profiles (within the impulse approximation) of H2, LiH, methane, water, acetylene, ethylene, ethane cyclopropane and cyclobutane have been calculated using the floating spherical Gaussian orbital (FSGO) wavefunctions. The agreement of the single-FSGO Compton profiles with the corresponding experimental or the Hartree-Fock (HF-SCF) theoretical ones is fairly good in most of the cases examined. The advantages and drawbacks of using the FSGO model for the calculation of Compton profiles are discussed
Quantum-information entropies for highly excited states of single-particle systems with power-type potentials
The asymptotics of the Boltzmann-Shannon information entropy as well as the Renyi entropy for the quantum probability density of a single-particle system with a confining (i.e., bounded below) power-type potential V(x)=x^2k with k∈N and x∈R, is investigated in the position and momentum spaces within the semiclassical (WKB) approximation. It is found that for highly excited states both physical entropies, as well as their sum, have a logarithmic dependence on its quantum number not only when k=1 (harmonic oscillator), but also for any fixed k. As a by-product, the extremal case k→∞ (the infinite well potential) is also rigorously analyzed. It is shown that not only the position-space entropy has the same constant value for all quantum states, which is a known result, but also that the momentum-space entropy is constant for highly excited states
An ab initio topographical investigation on the molecular electrostatic potential of some chemical mutagens
A detailed topographical investigation on the molecular electrostatic potentials (MESPs) of different conformers of acetaldehyde, nitrous acid and hydroxylamine has been carried out at the ab initio SCF level using TZ2p, 6-31G* and STO-3G basis sets. In general, large regions of negative potential have been observed. An attempt has been made to correlate these potentials with biological activities of the molecules. Mutagenic and toxicological properties appear to be related to the presence of these large negative zones
Free expansion of impenetrable bosons on one-dimensional optical lattices
We review recent exact results for the free expansion of impenetrable bosons
on one-dimensional lattices, after switching off a confining potential. When
the system is initially in a superfluid state, far from the regime in which the
Mott-insulator appears in the middle of the trap, the momentum distribution of
the expanding bosons rapidly approaches the momentum distribution of
noninteracting fermions. Remarkably, no loss in coherence is observed in the
system as reflected by a large occupation of the lowest eigenstate of the
one-particle density matrix. In the opposite limit, when the initial system is
a pure Mott insulator with one particle per lattice site, the expansion leads
to the emergence of quasicondensates at finite momentum. In this case,
one-particle correlations like the ones shown to be universal in the
equilibrium case develop in the system. We show that the out-of-equilibrium
behavior of the Shannon information entropy in momentum space, and its contrast
with the one of noninteracting fermions, allows to differentiate the two
different regimes of interest. It also helps in understanding the crossover
between them.Comment: 21 pages, 14 figures, invited brief revie
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