Theoretical and experimental investigations of photophysics of the nile red molecule and its protonated structures

Results of quantum-chemical studies of the nile red (NR) molecule and its protonated structures by the INDO/S method are presented. It is demonstrated that the best agreement between the calculated and experimental data is obtained for the flat molecule in the ground electron state. Energies of the strongest singlet and triplet electronic states, molecular nature of these states, transition oscillator force, dipole moments in the ground and excited states, electron density distribution around atoms and molecular fragments in the S₀ and S₁ states, and rate constants of radiative, internal, and intercombination conversion are presented for the NR molecule and its protonated structures. The most probable NR protonation centers are analyzed using the molecular electrostatic potential (MESP) method. It is established that the reaction of proton addition to the NR molecule proceeds at the cyclic nitrogen atom. As demonstrated the results of quantum-chemical calculations, low fluorescent properties of the protonated NR structures (with a quantum yield of 4%) are due to a high rate of the S₁ – T₄ intercombination conversion.     

钻具遇卡声波检测理论与实验研究*

石油钻探过程中,钻具经常发生陷入泥沙中不能自由活动进而卡在井下的事故。本文提出使用单发双收声系来检测钻具遇卡的方法,首先使用有限差分模拟了钻具外为自由流体和泥沙两种介质时的钻铤波响应,通过对比远近接收器的钻铤波衰减,发现泥沙卡钻情况下的钻铤波衰减要明显大于自由钻具情况。随后建立了实验模型对理论结果进行了验证。理论模拟与实验结果均表明声波方法可用以检测钻具遇卡事故,从而确定卡钻的深度位置,为解卡钻作业提供解释依据。     

Theoretical predictions of enforced structural changes in molecules

A very simple quantum chemical model is proposed to simulate the effect of external forces acting on a single molecule. It involves optimising the geometry of a molecule with an external force applied to selected nuclei. This approach is used to investigate conformational transitions of the pyranose ring, which have been the subject of several atomic force microscopy (AFM) experiments, and to generate a number of previously unknown isomers of azobenzene.     

Realistic predictions for the detection of supersymmetric dark matter

We present new predictions for the detection of supersymmetric dark matter via its annihilation in the Sun and elastic scattering off heavy nuclei in the laboratory. Our predictions include many effects found in realistic models such as non-degenerate left- and right-squark masses, unequal supersymmetric Higgs v.e.v.s and photino/higgsino/zino mixing in the lightest supersymmetric particle (LSP). Hadronic matrix elements are estimated using either the naive quark model or the EMC measurement of the spin-dependent proton structure function and perturbative QCD. Nuclear matrix elements are calculated using the shell-model and the small effects of quark vector current operators are discussed. Previous predictions for the elastic LSP-proton scattering cross section, and hence for high energy solar neutrinos from LSP annihilations, are reduced by the EMC estimate and by unequal squark masses, but may be increased by unequal Higgs v.e.v.s. Previous predictions for elastic photino scattering off nuclei with unpaired neutrons are greatly enhanced by the EMC estimate. As a result, preferences for the nuclei to be used in laboratory experiments to detect supersymmetric dark matter may be greatly altered.     

Model predictions and experimental characterization of Co-Pt alloy clusters

Model and real cobalt-platinum alloy clusters are compared in terms of structure, composition and segregation. Canonical and semi grand canonical Metropolis Monte Carlo simulations are performed to model these clusters, using embedded atom (EAM) and modified embedded atom (MEAM) potentials. All of them correctly predict the bulk L1₂ Co₃Pt and CoPt₃ structures as well as the L1₀ CoPt phase. However, the lattice parameters, phase stability and the L1₀-fcc order-disorder transition temperature are at variance. Segregation predictions with EAM and MEAM potentials are contradictory. Experimentally, mixed clusters with various compositions were deposited by Low Energy Cluster Beam on amorphous carbon at room temperature. Their size distribution, crystalline structure and composition were examined by Transmission Electron Microscopy (TEM). Clusters with the same size distributions were modelled. Both experiment and modelling show their crystallographic parameters to continuously correspond to the fcc CoPt chemically disordered phase. Diffraction measurements indicate surface segregation of the specie in excess, in agreement with EAM predictions for the Co-rich phase. The consequences on magnetic properties are discussed.     

Coexistence of superconductivity and magnetism theoretical predictions and experimental results

Superconductivity and ferromagnetic ordering are two antagonistic types of ordering, and their mutual influence leads to many interesting phenomena which have been studied recently in ternary compounds. Theoretical analysis of ferromagnetic materials which are type II superconductors near the superconducting transition point T _cl shows that they become type I near the magnetic transition point T _M. The proposed theory constructed for the case T _M « T _cl predicts the formation of a transverse domain-like (DS phase) magnetic structure below T _M. The electronic spectrum appears to be gapless in the DS phase of clean compounds with a re-entrant transition. The change from type II to type I behaviour as the sample is cooled to T _M has been observed in ErRh₄B₄. Experimental data for HoMo₆S₈, HoMo₆Se₈ and ErRh₄B₄ give evidence for the coexistence of super-conductivity and non-uniform magnetic ordering below T _M. Mutual influence of superconducting and magnetic orderings is also studied.     

Theoretical predictions about ENDOR of biradicals in liquid solution

Starting from the equation of motion for the density matrix, ENDOR spectra are computed for a biradical for the first time. The model biradical carries two electronic spins S = 1/2 and two nuclear spins I = 1/2. The relaxation operator is calculated ab initio for three distinct relaxation mechanisms. These mechanisms are the modulation of the isotropic exchange interaction, the hyperfine tensor and the zero-field splitting tensor. The dependence of the ENDOR effect on the amplitudes of the radiofrequency and microwave fields, on the strength of the zero-field splitting tensor, and on the correlation times of the correlation functions is investigated.     

Optogalvanic detection of NaNe molecule

Summary The formation of NaNe molecule has been detected in a hollow cathode lamp containing traces of sodium and neon using the optogalvanic technique. Two broad continuum peaks have been observed in the structure. They have been analysed to result due to transitions {Na(3s) + Ne(2p ⁶)}²Σ¹→ →{Na*(3p) + Ne(2p ⁶)}²Π,²Σ and {Na*(3p) + Ne(2p ⁶)}²Π,²Σ→{Na*(5s) + Ne(2p ⁶)}²Σ¹. A third peak in between these is probably due to a two-photon transition from 3s→5s of Na in NaNe. The authors of this paper have agreed to not receive the proofs for correction.     

Theoretical simulation of the fluorescence spectrum of a single molecule

The possibility of computer simulation of the fluorescence spectrum of an actual system of single molecules, whose initial isomeric structure is photochemically transformed as a result of a radiationless resonance transition, is demonstrated.Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 71, No. 6, pp. 740–744, November–December, 2004.This revised version was published online in April 2005 with a corrected cover date.     

Theoretical infrared transition matrix elements for the water molecule

Using the Hartree-Fock-Roothaan method, symmetric potential energy and dipole moment functions have been obtained for the ground state of the water molecule. These functions were transformed and analyzed in terms of the normal symmetric stretching (v₁) and bending (v₂) coordinates for the calculation of i.r. transition matrix elements. There is satisfactory agreement between this work and the experimental values for the transition matrix element of the v₂ fundamental. However, a discrepancy of a factor of 2.5 is observed between calculated and experimental matrix elements for the v₁ fundamental.     

Theoretical study on lower electronic states of the FeSi molecule

The low lying electronic states of the FeSi molecule have been investigated by performing complete active space self-consistent field (CASSCF) and multireference single and double excitation configuration interaction (MRSDCI) calculations. Although the classification of the ground state was not established, the results of the MRSDCI calculations suggest that the ground state of FeSi is ³Δ, and the lowest excited state is ⁵Π whose transition energy is 0.36 eV including the Davidson-type Q correction. The R _e given by MRSDCI with Q correction is 2.23 Å for ³Δ and 2.19 Å for ⁵Π. The spectroscopic constants and dipole moments of the low lying ⁵Δ and ³Π states as well as the ³Δ and ⁵Π states are also evaluated. The bonding nature of FeSi in the ³Δ state is discussed in comparison with the FeC molecule.     

Theoretical predictions of diffusion from Brownian motion in superstrong polymers

This paper presents a summary of unique highly nonlinear static and dynamic theories for chain molecules (actually, for almost any kind of organic molecule), including the first superstrong polymers. These theories have been used to predict and explain (1) the physical self-assembly (self-ordering) of specific kinds of molecules into liquid crystalline (LC) phases (i.e., partially ordered phases) and (2) the diffusion of these molecules in various LC phases and the isotropic (I) liquid phase.By acceptance of this article, the publisher recognizes that the U. S. Government retains a nonexclusive, royality-free license to publish or reproduce the published form of this contribution, or to allow others to do so, for U.S. Government purposes.     

Theoretical study of highly-excited states of KRb molecule

Semi-empirical adiabatic potential energy curves of highly excited states of the KRb molecule are calculated as a function of the internuclear distance R over a wide range from 3 to 150 a ₀. The diatomic molecule is treated as an effective two-electron system by using the large core pseudopotentials and core polarization potentials. All calculations are performed by using the nonrelativistic CASSCF/MRCI method with accurate basis set functions. The spectroscopic constants of the calculated electronic states agree well with experimental data, including the recent ones from Lee et al., and with available theoretical results.     

Quantitative comparison between theoretical predictions and experimental results for the BCS-BEC crossover

Theoretical predictions for the Bardeen-Cooper-Schrieffer-Bose-Einstein condensation crossover of trapped Fermi atoms are compared with recent experimental results for the density profiles of 6Li. The calculations rest on a single theoretical approach that includes pairing fluctuations beyond mean-field. Excellent agreement with experimental results is obtained. Theoretical predictions for the zero-temperature chemical potential and gap at the unitarity limit are also found to compare extremely well with Quantum Monte Carlo simulations and with recent experimental results.     

Microscopy and single molecule detection in photosynthesis

Progress in various fields of microscopy techniques brought up enormous possibilities to study the photosynthesis down to the level of individual pigment-protein complexes. The aim of this review is to present recent developments in the photosynthesis research obtained using such highly advanced techniques. Three areas of microscopy techniques covering optical microscopy, electron microscopy and scanning probe microscopy are reviewed. Whereas the electron microscopy and scanning probe microscopy are used in photosynthesis mainly for structural studies of photosynthetic pigment-protein complexes, the optical microscopy is used also for functional studies.     

Theoretical study of two-proton radioactivity. Status,predictions, and applications

In this paper the survey of the current state of investigation of two-proton radioactivity and related processes (three-body decays) is presented. The three-body (core + p + p) theoretical model of two-proton radioactivity based on the hyperspherical harmonics method and approximate boundary conditions of the Coulomb’s three-body problem specific for the studied class of processes is considered. The predictions for lifetimes and correlations of decay products for “promising” two-proton emitters are given. Astrophysical applications of the theory of two-proton radioactivity are discussed.     

Mechanical properties of carbon nanotubes: theoretical predictions and experimental measurements

Mechanical properties of carbon nanotubes are discussed based on recent advances in both modeling and experiment. To cite this article: R.S. Ruoff et al., C. R. Physique 4 (2003).