Density-matrix renormalization-group study of low-lying excitations of polyacene within a Pariser-Parr-Pople model

We have carried out symmetrized density-matrix renormalization-group calculations to study the nature of excited states of long polyacene oligomers within a Pariser-Parr-Pople Hamiltonian. We have used the C-2 symmetry, the electron-hole symmetry, and the spin parity of the system in our calculations. We find that there is a crossover in the lowest dipole forbidden two-photon state and the lowest dipole allowed excited state with size of the oligomer. In the long system limit, the two-photon state lies below the lowest dipole allowed excited state. The triplet state lies well below the two-photon state and energetically does not correspond to its description as being made up of two triplets. These results are in agreement with the general trends in linear conjugated polymers. However, unlike in linear polyenes wherein the two-photon state is a localized excitation, we find that in polyacenes, the two-photon excitation is spread out over the system. We have doped the systems with a hole and an electron and have calculated the charge excitation gap. Using the charge gap and the optical gap, we estimate the binding energy of the 1(1)B(-) exciton to be 2.09 eV. We have also studied doubly doped polyacenes and find that the bipolaron in these systems, to be composed of two separated polarons, as indicated by the calculated charge-density profile and charge-charge correlation function. We have studied bond orders in various states in order to get an idea of the excited state geometry of the system. We find that the ground state, the triplet state, the dipole allowed state, and the polaron excitations correspond to lengthening of the rung bonds in the interior of the oligomer while the two-photon excitation corresponds to the rung bond lengths having two maxima in the system.

Direct and sensitized (energy and electron transfer) geometric isomerization of stilbene within zeolites: a comparison between solution and zeolite as reaction media

The trans- and cis-stilbenes upon inclusion in NaY zeolite are thermally stable. Direct excitation and triplet sensitization results in geometric isomerization and the excited state behavior under these conditions are similar to that in solution. Upon direct excitation, a photostationary state consisting of 65% cis and 35% trans isomers is established. Triplet sensitization with 2-acetonaphthone gave a photostationary state consisting of 63% cis and 37% trans isomers. These numbers are similar to the ones obtained in solution. Thus, the presence of cations and the confined space within the zeolite have very little influence on the overall chemistry during direct and triplet sensitization. However, upon electron transfer sensitization with N-methylacridinium (NMA) as the sensitizer within NaY, isomerization from cis-stilbene radical cation to trans-stilbene occurs and the recombination of radical ions results in triplet stilbene. Prolonged irradiation gave a photostationary state (65% cis and 35% trans) similar to triplet sensitization. This behavior is unique to the zeolite and does not take place in solution. Steady state fluorescence measurements showed that the majority of stilbene molecules are close to the N-methylacridinium sensitizer. Diffuse reflectance flash photolysis studies established that independent of the isomer being sensitized only trans radical cation is formed. Triplet stilbene is believed to be generated via recombination of stilbene radical cation and sensitizer radical anion. One should be careful in using acidic HY zeolite as a medium for photoisomerization of stilbenes. In our hands, in these acidic zeolites isomerization dominated the photoisomerization. (C) 2002 Elsevier Science B.V. All rights reserved.

Electrochemical studies of polyaniline in a gel polymer electrolyte - High energy and high power characteristics of a solid-state redox supercapacitor

Studies on redox supercapacitors employing electronically conducting polymers are of great importance for hybrid power sources and pulse power applications. In the present study, polyaniline (PANI) has been potentiodynamically deposited on stainless steel substrate and characterized in a gel polymer electrolyte (GPE). Use of the GPE facilitates a voltage limit of the capacitor to 1 V, instead of 0.75 V in aqueous electrolytes. From charge-discharge studies of the solid-state PANI capacitors, a specific capacitance of 250 F g(-1) has been obtained at a specific power of 7.5 kW kg(-1) of PANI. The values of specific capacitance and specific power are considerably higher than those reported in the literature. High energy and high power characteristics of the PANI are presented. (C) 2002 The Electrochemical Society.

Electrochemical tuning and mechanical resilience of single-wall carbon nanotubes

Single-wall carbon nanotubes (SWNTs) are fascinating systems exhibiting many novel physical properties. In this paper, we give a brief review of the structural, electronic, vibrational, and mechanical properties of carbon nanotubes. In situ resonance Raman scattering of SWNTs investigated under electrochemical biasing demonstrates that the intensity of the radial breathing mode varies significantly in a nonmonotonic manner as a function of the cathodic bias voltage, but does not change appreciably under anodic bias. These results can be quantitatively understood in terms of the changes in the energy gaps between the 1 D van Hove singularities in the electron density of states, arising possibly due to the alterations in the overlap integral of pi bonds between the p-orbitals of the adjacent carbon atoms. In the second part of this paper, we review our high-pressure X-ray diffraction results, which show that the triangular lattice of the carbon nanotube bundles continues to persist up to similar to10 GPa. The lattice is seen to relax just before the phase transformation, which is observed at similar to10 GPa. Further, our results display the reversibility of the 2D lattice symmetry even after compression up to 13 GPa well beyond the 5 GPa value observed recently. These experimental results explicitly validate the predicted remarkable mechanical resilience of the nanotubes.

Energy released during arc crack propagation

The problem of circular arc cracks in a homogeneous medium is revisited. An unusual but simple method to calculate the energy change due to arc crack propagation along a circle is illustrated based on the earlier work of Sih and Liebowitz (1968). The limiting case of crack of angle 27pi is shown to correspond with the problem of a circular hole in a large plate under remote loading.

Energy transfer efficiency distributions in polymers in solution during folding and unfolding

Distribution of fluorescence resonance energy transfer (FRET) efficiency between the two ends of a Lennard-Jones polymer chain both at equilibrium and during folding and unfolding has been calculated, for the first time, by Brownian dynamics simulations. The distribution of FRET efficiency becomes bimodal during folding of the extended state subsequent to a temperature quench, with the width of the distribution for the extended state broader than that for the folded state. The reverse process of unfolding subsequent to a upward temperature jump shows different characteristics. The distributions show significant viscosity dependence which can be tested against experiments.

DNA Free Energy-Based Promoter Prediction and Comparative Analysis of Arabidopsis and Rice Genomes

The cis-regulatory regions on DNA serve as binding sites for proteins such as transcription factors and RNA polymerase. The combinatorial interaction of these proteins plays a crucial role in transcription initiation, which is an important point of control in the regulation of gene expression. We present here an analysis of the performance of an in silico method for predicting cis-regulatory regions in the plant genomes of Arabidopsis (Arabidopsis thaliana) and rice (Oryza sativa) on the basis of free energy of DNA melting. For protein-coding genes, we achieve recall and precision of 96% and 42% for Arabidopsis and 97% and 31% for rice, respectively. For noncoding RNA genes, the program gives recall and precision of 94% and 75% for Arabidopsis and 95% and 90% for rice, respectively. Moreover, 96% of the false-positive predictions were located in noncoding regions of primary transcripts, out of which 20% were found in the first intron alone, indicating possible regulatory roles. The predictions for orthologous genes from the two genomes showed a good correlation with respect to prediction scores and promoter organization. Comparison of our results with an existing program for promoter prediction in plant genomes indicates that our method shows improved prediction capability.

Fracture energy and softening behavior of high-strength concrete

An experimental investigation on the fracture properties of high-strength concrete (HSC) is reported. Three-point bend beam specimens of size 100 x 100 x 500 mm were used as per RILEM-FMC 50 recommendations. The influence of maximum size of coarse aggregate on fracture energy, fracture toughness, and characteristic length of concrete has been studied. The compressive strength of concrete ranged between 40 and 75 MPa. Relatively brittle fracture behavior was observed with the increase in compressive strength. The load-CMOD relationship is linear in the ascending portion and gradually drops off after the peak value in the descending portion. The length of the tail end portion of the softening curve increases as the size of coarse aggregate increases. The fracture energy increases as the maximum size of coarse aggregate and compressive strength of concrete increase. The characteristic length of concrete increases with the maximum size of coarse aggregate and decreases as the compressive strength increases, (C) 2002 Elsevier Science Ltd. All rights reserved.

Freezing of classical fluids in a quenched random potential

The phase diagram of a hard-sphere fluid in the presence of a random pinning potential is studied analytically and numerically. In the analytic work, replicas are introduced for averaging over the quenched disorder, and the hypernetted chain approximation is used to calculate density correlations in the replicated liquid. The freezing transition of the liquid into a nearly crystalline state is studied using a density-functional approach, and the liquid to glass transition is studied using a phenomenological replica symmetry breaking approach. In the numerical work, local minima of a discretized version of the Ramakrishnan-Yussouff free-energy functional are located and the phase diagram in the density-disorder plane is obtained from an analysis of the relative stability of these minima. Both approaches lead to similar results for the phase diagram. The first-order liquid to crystalline solid transition is found to change to a continuous liquid to glass transition as the strength of the disorder is increased above a threshold value.

Ratchet for energy transport between identical reservoirs

A one-dimensional periodic array of elastically colliding hard points, with a noncentrosymmetric unit cell, connected at its two ends to identical but nonthermal energy reservoirs, is shown to carry a sustained unidirectional energy current.

Symmetry-breaking transitions in equilibrium shapes of coherent precipitates: Effect of elastic anisotropy and inhomogeneity

We examine the symmetry-breaking transitions in equilibrium shapes of coherent precipitates in two-dimensional (2-D) systems under a plane-strain condition with the principal misfit strain components epsilon(xx)*. and epsilon(yy)*. For systems with cubic elastic moduli, we first show all the shape transitions associated with different values of t = epsilon(yy)*/epsilon(xx)*. We also characterize each of these transitions, by studying its dependence on elastic anisotropy and inhomogeneity. For systems with dilatational misfit (t = 1) and those with pure shear misfit (t = -1), the transition is from an equiaxed shape to an elongated shape, resulting in a break in rotational symmetry. For systems with nondilatational misfit (-1 < t < 1; t not equal 0), the transition involves a break in mirror symmetries normal to the x- and y-axes. The transition is continuous in all cases, except when 0 < t < 1. For systems which allow an invariant line (-1 less than or equal to t < 0), the critical size increases with an increase in the particle stiffness. However, for systems which do not allow an invariant line (0 < t less than or equal to 1), the critical size first decreases, reaches a minimum, and then starts increasing with increasing particle stiffness; moreover, the transition is also forbidden when the particle stiffness is greater than a critical value.

The origin of degeneracies and crossings in the 1d Hubbard model

The paper is devoted to the connection between integrability of a finite quantum system and degeneracies of its energy levels. In particular, we analyse in detail the energy spectra of finite Hubbard chains. Heilmann and Lieb demonstrated that in these systems there are crossings of levels of the same parameter-independent symmetry. We show that this apparent violation of the Wigner-von Neumann noncrossing rule follows directly from the existence of nontrivial conservation laws and is a characteristic signature of quantum integrability. The energy spectra of Hubbard chains display many instances of permanent (at all values of the coupling) twofold degeneracies that cannot be explained by parameter-independent symmetries. We relate these degeneracies to the different transformation properties of the conserved currents under spatial reflections and the particle-hole transformation and estimate the fraction of doubly degenerate states. We also discuss multiply degenerate eigenstates of the Hubbard Hamiltonian. The wavefunctions of many of these states do not depend on the coupling, which suggests the existence of an additional parameter-independent symmetry.

A molecular dynamics study based post facto free energy analysis of the binding of bovine angiogenin with UMP and CMP ligands

Angiogenin is a protein belonging to the superfamily of RNase A. The RNase activity of this protein is essential for its angiogenic activity. Although members of the RNase A family carry out RNase activity, they differ markedly in their strength and specificity. In this paper, we address the problem of higher specificity of angiogenin towards cytosine against uracil in the first base binding position. We have carried out extensive nano-second level molecular dynamics(MD) computer simulations on the native bovine angiogenin and on the CMP and UMP complexes of this protein in aqueous medium with explicit molecular solvent. The structures thus generated were subjected to a rigorous free energy component analysis to arrive at a plausible molecular thermodynamic explanation for the substrate specificity of angiogenin.

Effect of orientational motion of mobile chromophores on the dynamics of Forster energy transfer in polymers

Brownian dynamics (BD) simulations have been carried out to explore the effects of the orientational motion of the donor-acceptor (D-A) chromophore pair on the Forster energy transfer between the D-A pair embedded in a polymer chain in solution. It is found that the usually employed orientational averaging (that is, replacing the orientational factor, kappa, by kappa (2) = 2/3) may lead to an error in the estimation of the rate of the reaction by about 20%. In the limit of slow orientational relaxation, the preaveraging of the orientational factor leads to an overestimation of the rate, while in the opposite limit of very fast orientational relaxation, the usual scheme underestimates the rate. The latter results from an interesting interplay between reaction and diffusion. On the other hand, when one of the chromophores is fixed, the preaveraged rate is found to be fairly reliable if the rotational relaxation of the chromophore is sufficiently fast. The present study also reveals a power law dependence of the FRET rate on the chain length (rate proportional to N- alpha, with alpha approximate to 2.6).

Electronic structure of ${\rm Ca}_{1-x}{\rm Sr}_x{\rm VO}_3$: A tale of two energy scales

We investigate the electronic structure of Ca1-xSrxVO3 using photoemission spectroscopy. Core level spectra establish an electronic phase separation at the surface, leading to a distinctly different surface electronic structure compared to the bulk. Analysis of the photoemission spectra of this system allowed us to separate the surface and bulk contributions. These results help us to understand properties related to two vastly differing energy scales, namely the low-energy scale of thermal excitations ( $\sim\!k_{\rm B}T$) and the high-energy scale related to Coulomb and other electronic interactions.