Mixed Quantum/Classical Approach for Description of Molecular Collisions in Astrophysical Environments

An efficient and accurate mixed quantum/classical theory approach for computational treatment of inelastic scattering is extended to describe collision of an atom with a general asymmetric-top rotor polyatomic molecule. Quantum mechanics, employed to describe transitions between the internal states of the molecule, and classical mechanics, employed for description of scattering of the atom, are used in a self-consistent manner. Such calculations for rotational excitation of HCOOCH3 in collisions with He produce accurate results at scattering energies above 15 cm–1, although resonances near threshold, below 5 cm–1, cannot be reproduced. Importantly, the method remains computationally affordable at high scattering energies (here up to 1000 cm–1), which enables calculations for larger molecules and at higher collision energies than was possible previously with the standard full-quantum approach. Theoretical prediction of inelastic cross sections for a number of complex organic molecules observed in space becomes feasible using this new computational tool

Mixed Quantum/Classical Calculations of Total and Differential Elastic and Rotationally Inelastic Scattering Cross Sections for Light and Heavy Reduced Masses in a Broad Range of Collision Energies

The mixed quantum/classical theory (MQCT) for rotationally inelastic scattering developed recently [A. Semenov and D. Babikov, J. Chem. Phys.139, 174108 (2013)] is benchmarked against the full quantum calculations for two molecular systems: He + H2 and Na + N2. This allows testing new method in the cases of light and reasonably heavy reduced masses, for small and large rotational quanta, in a broad range of collision energies and rotational excitations. The resultant collision cross sections vary through ten-orders of magnitude range of values. Both inelastic and elastic channels are considered, as well as differential (over scattering angle) cross sections. In many cases results of the mixed quantum/classical method are hard to distinguish from the full quantum results. In less favorable cases (light masses, larger quanta, and small collision energies) some deviations are observed but, even in the worst cases, they are within 25% or so. The method is computationally cheap and particularly accurate at higher energies, heavier masses, and larger densities of states. At these conditions MQCT represents a useful alternative to the standard full-quantum scattering theory

Anisotropic relaxation in NADH excited states studied by polarization-modulation pump-probe transient spectroscopy

We present the results of experimental and theoretical studies of fast anisotropic relaxation and rotational diffusion in the first electron excited state of biological coenzyme NADH in water-ethanol solutions. The experiments have been carried out by means of a novel polarization-modulation transient method and fluorescence polarization spectroscopy. For interpretation of the experimental results a model of the anisotropic relaxation in terms of scalar and vector properties of transition dipole moments and based on the Born-Oppenheimer approximation has been developed. The results obtained suggest that the dynamics of anisotropic rovibronic relaxation in NADH under excitation with 100~fs pump laser pulses can be characterised by a single vibration relaxation time $\tau_v$ laying in the range 2--15~ps and a single rotation diffusion time $\tau_r$ laying in the range 100--450~ps a subject of ethanol concentration. The dependence of the times $\tau_v$ and $\tau_r$ on the solution polarity (static permittivity) and viscosity has been determined and analyzed. Limiting values of an important parameter $\langle P_2(\cos\theta(t))\rangle$ describing the rotation of the transition dipole moment in the course of vibrational relaxation has been determined from experiment as function of the ethanol concentration and analyzed.Comment: 14 pages, 13 figure

Bootstrap and the physical values of πN\pi N resonance parameters

This is the 6th paper in the series developing the formalism to manage the effective scattering theory of strong interactions. Relying on the theoretical scheme suggested in our previous publications we concentrate here on the practical aspect and apply our technique to the elastic pion-nucleon scattering amplitude. We test numerically the pion-nucleon spectrum sum rules that follow from the tree level bootstrap constraints. We show how these constraints can be used to estimate the tensor and vector $NN\rho$ coupling constants. At last, we demonstrate that the tree-level low energy expansion coefficients computed in the framework of our approach show nice agreement with known experimental data. These results allow us to claim that the extended perturbation scheme is quite reasonable from the computational point of view.Comment: 41 pages, 7 figure

Accurate Calculations of Rotationally Inelastic Scattering Cross Sections Using Mixed Quantum/Classical Theory

For computational treatment of rotationally inelastic scattering of molecules, we propose to use the mixed quantum/classical theory, MQCT. The old idea of treating translational motion classically, while quantum mechanics is used for rotational degrees of freedom, is developed to the new level and is applied to Na + N2 collisions in a broad range of energies. Comparison with full-quantum calculations shows that MQCT accurately reproduces all, even minor, features of energy dependence of cross sections, except scattering resonances at very low energies. The remarkable success of MQCT opens up wide opportunities for computational predictions of inelastic scattering cross sections at higher temperatures and/or for polyatomic molecules and heavier quenchers, which is computationally close to impossible within the full-quantum framework

Simulation models and research algorithms of thin shell structures deformation Part I. Shell deformation models

In the article the development of thin shell construction theory is considered according to the contribution of researchers, chronology, including the most accurate and simplified solutions. The review part of the article consists only of those publications which are related to the development of shell theory. The statement is based on the works of famous Russian researchers (V. V. Novozhilov, A. I. Lurie, A. L. Goldenweiser, H. M. Mushtari, V. Z. Vlasov), who developed the specified theory the most. The paper also mentions the researchers who improved the theory, calculation methods in aspects of strength, sustainability and vibrations of thin elastic shell constructions. Separately the application of the models for ribbed shells constructions is shown. It is reporting the basic principles of nonlinear thin shell construction theory development, including the nonlinear relations for deformations. In the article it is shown that if median surface of the shell is referred to the orthogonal coordinate system, then the expressions for deformations, obtained by different authors, practically correspond. The case in which the median surface of the shell is referred to an oblique-angled coordinate system was developed by A. L. Goldenweiser. For static problem, the functional of the total potential energy of deformation, representing the difference between the potential energy and the work of external forces, is used. The equilibrium equations and natural boundary conditions are derived from the minimum condition of this functional. In case of dynamic problem, the functional of the total deformation energy of the shell is described in which it is necessary to consider the kinetic energy of shell deformation. It is necessary to underline that the condition for minimum of the specified functional lets to derive the movement equations and natural boundary and initial conditions. Also, in the article the results of contemporary research of thin shell theory are presented

Searching for a BNP standard: Glycosylated proBNP as a common calibrator enables improved comparability of commercial BNP immunoassays

AbstractBackgroundCirculating B-type natriuretic peptide (BNP) is widely accepted as a diagnostic and risk assessment biomarker of cardiac function. Studies suggest that there are significant differences in measured concentrations among different commercial BNP immunoassays. The purpose of our study was to compare BNP-related proteins to determine a form that could be used as a common calibrator to improve the comparability of commercial BNP immunoassay results.MethodsBNP was measured in 40 EDTA-plasma samples from acute and chronic heart failure patients using five commercial BNP assays: Alere Triage, Siemens Centaur XP, Abbott I-STAT, Beckman Access2 and ET Healthcare Pylon. In parallel with internal calibrators from each manufacturer, six preparations containing BNP 1–32 motif a) synthetic BNP, b) recombinant BNP (E. coli), c) recombinant nonglycosylated proBNP (E. coli), d) recombinant His-tagged (N-terminal) nonglycosylated proBNP (E. coli), e) recombinant glycosylated proBNP (HEK cells), and f) recombinant glycosylated proBNP (CHO cells) were also used as external calibrators for each assay.ResultsUsing the internal standards provided by manufacturers and for five of six external calibrators, up to 3.6-fold differences (mean 1.9-fold) were observed between BNP immunoassays (mean between-assay CV 24.5–47.2%). A marked reduction of the between-assay variability was achieved, when glycosylated proBNP expressed in HEK cells was used as the common calibrator for all assays (mean between-assay CV 14.8%).ConclusionsOur data suggest that recombinant glycosylated proBNP could serve as a common calibrator for BNP immunoassays to reduce between-assay variability and achieve better comparability of BNP concentrations of commercial BNP immunoassays

Influence of the ocean surface temperature and sea ice concentration on regional climate changes in Eurasia in recent decades

Numerical experiments with the ECHAM5 atmospheric general circulation model have been performed in order to simulate the influence of changes in the ocean surface temperature (OST) and sea ice concentration (SIC) on climate characteristics in regions of Eurasia. The sensitivity of winter and summer climates to OST and SIC variations in 1998-2006 has been investigated and compared to those in 1968-1976. These two intervals correspond to the maximum and minimum of the Atlantic Long-Period Oscillation (ALO) index. Apart from the experiments on changes in the OST and SIC global fields, the experiments on OST anomalies only in the North Atlantic and SIC anomalies in the Arctic for the specified periods have been analyzed. It is established that temperature variations in Western Europe are explained by OST and SIC variations fairly well, whereas the warmings in Eastern Europe and Western Siberia, according to model experiments, are substantially (by a factor of 2-3) smaller than according to observational data. Winter changes in the temperature regime in continental regions are controlled mainly by atmospheric circulation anomalies. The model, on the whole, reproduces the empirical structure of changes in the winter field of surface pressure, in particular, the pressure decrease in the Caspian region; however, it substantially (approximately by three times) underestimates the range of changes. Summer temperature variations in the model are characterized by a higher statistical significance than winter ones. The analysis of the sensitivity of the climate in Western Europe to SIC variations alone in the Arctic is an important result of the experiments performed. It is established that the SIC decrease and a strong warming over the Barents Sea in the winter period leads to a cooling over vast regions of the northern part of Eurasia and increases the probability of anomalously cold January months by two times and more (for regions in Western Siberia). This effect is caused by the formation of the increased-pressure region with a center over the southern boundary of the Barents Sea during the SIC decrease and an anomalous advection of cold air masses from the northeast. This result indicates that, to estimate the ALO actions (as well as other long-scale climatic variability modes) on the climate of Eurasia, it is basically important to take into account (or correctly reproduce) Arctic sea ice changes in experiments with climatic models