Simulation of photoelectron spectra using the reflection principle in combination with unrestricted excitation ADC2 to assess the accuracy of excited-state calculations

The gas-phase photoelectron spectra of ethene, formaldehyde, formic acid and difluoromethane are simulated using the reflection principle and the unrestricted second-order algebraic diagrammatic construction [UADC(2)] scheme of the polarization propagator for the computation of the vertical-excited states of the cations at the equilibrium geometry of the parent neutral molecule. Comparison is made with experimental spectra and the established highly accurate ionization IP-ADC(3) theory to gain insight into the accuracy and applicability of recently developed excitation UADC schemes. Within UADC(2), we distinguish between the strict and extended schemes UADC(2)-s and UADC(2)-x. While the latter approach is found to slightly underestimate the experimental photoelectron spectra by 0.3 eV and can thus be regarded as a reliable scheme within the limits of the applied reflection principle and the underlying approximations, the UADC(2)-s scheme tends to overestimate the excitation energies by about 0.5 eV. Time-dependent density functional theory is also applied in combination with the standard B3LYP xc functional and turns out to be a useful computational tool for the simulation of the photoelectron spectra of the studied species.     

Novel covalent bond in proteins: calculations on model systems question the bond stability

We have investigated the sulfilimine covalent link between methionine (Met) and lysine (Lys), recently identified in collagen IV (R. Vanacore, A.-J. L. Ham, M. Voehler, C. R. Sanders, T. P. Conrads, T. D. Veenstra, K. B. Sharpless, P. E. Dawson, B. G. Hudson, Science 2009, 325, 1230), and have explored its stability with respect to both the redox processes and UV radiation by means of advanced computational methods. We have concluded that the bond should be present in a protonated state, (-NH=S-)(+). The bond is characterized by a relatively high standard reduction potential, that is, the bond should not be stable in a typical cell environment; if the sulfilimine bond exists (as suggested by the experiment) then the bond has to be supported by the protein environment. The sulfilimine bond then destabilizes the protein structure with respect to the alternative tertiary structure. We discuss conditions under which the bond could be formed as well as other possible structural arrangements consistent with the Met-Lys stoichiometry; some of the alternative bond motifs are more thermodynamically stable than the sulfilimine bond. We suggest that the character of the Met-Lys contact could be approached via NEXAFS spectroscopy. Finally, we show that the protonation brings photostability to the sulfilimine bond.     

Log-gases on quadratic lattices via discrete loop equations and q-boxed plane partitions

We study a general class of log-gas ensembles on (shifted) quadratic lattices. We prove that the corresponding empirical measures satisfy a law of large numbers and that their global fluctuations are Gaussian with a universal covariance. We apply our general results to analyze the asymptotic behavior of a q-boxed plane partition model introduced by Borodin, Gorin and Rains. In particular, we show that the global fluctuations of the height function on a fixed slice are described by a one-dimensional section of a pullback of the two-dimensional Gaussian free field.Our approach is based on a q-analogue of the Schwinger–Dyson (or loop) equations, which originate in the work of Nekrasov and his collaborators, and extends the methods developed by Borodin, Gorin and Guionnet to quadratic lattices.     

Computational identification of interface delaminations in layered composites based on surface measurements

One of the main contemporary challenges facing engineering sciences is how to identify the actual state of internal defects, their self-organized criticality, interaction, and thus influence on the overall strength and durability of a system. In this study we address one aspect in the panoply of problems emerging in this context, namely: how to identify a single delamination in a layered composite specimen performing measurements only on the surface. In rigor terms the answer to this question relates to the answer to the question of how to solve the nonlinear semi-inverse problem of the mathematical programming emerging from the minimization of an associated Kohn–Vogelius functional with respect to some set of design variables parameterizing the delamination region. Clearly, one methodological way to approach the solution is to use some classical, gradient-based, nonlinear programming technique, like SQP. One should not forget, however, that the identification problems of this class are per se ill-posed, nonsmooth, and highly sensitive to the initial boundary data. Three bottlenecks occur that cannot be trivially circumvented when the shape of the delamination region, its characteristic dimensions, and position are preliminarily unknown (or highly uncertain). Based on an appropriate split of the governing Kohn–Vogelius functional we succeed here in transforming the ill-posed local inverse problem into a coupled system of elliptic well-posed Euler–Lagrange equations and to derive a direct smooth iterative strategy for its numerical solution. The strategy leads to a semiempirical reconstruction method for finding isolated interlaminar cavities from the measurement of the displacement field performed on the surface of the specimen.     

сОДЕРжАНИь РАБОт, ОпУБлИкОВАННых тОлькО В ЧЕшскОМ ИжДАНИИ НАстОьЩЕгО жУРНАлА

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Abstracts of Papers which have appeared only in the Czech Edition of this Journal

     

The effect of supermolecular structure on some electric properties of layers of poly(N-vinylcarbazole)

Current-voltage characteristics were measured for sandwich samples of poly(N-vinylcarbazole) amorphous layers and layers with pronounced supermolecular structure, similar to the fibrillar structure. Analysis of the superlinear regions of the current-voltage dependences of 3–35 μm thick samples with fibrillar structure showed that the effects of space charge are important. Results obtained for amorphous layers agree with an earlier interpretation of the current-voltage curves based on the Poole-Frenkel effect.     

Marcelin-de Donder kinetics near equilibrium

A linear approximation for the Marcelin-de Donder kinetics (MC) near the point of detailed equilibrium (p.d.e./is studied. In particular it is shown that in the invariant plane the p.d.e. is stable knot.

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Nuclear magnetic resonance studies of internal rotation—III Rotational barriers in META- and PARA-substituted N,N-dimethylcinnamamides

The rotational barriers about the C? N bond of eight m- and p-substituted N, N-dimethyl cinnamamides have been determined by the iterative total line shape NMR method. The ΔG values have been correlated with the substituent constants σ, σⁿ and σ⁺. By comparison of the results with literature data, some conclusions about the accuracy of the barrier determination as well as the transmittance of polar effects in conjugated amides have been drawn.     

New types of nonclassical iridium carbonyls formed in Ir-ZSM-5: a Fourier transform infrared spectroscopy investigation

In this work we report some new nonclassical carbonyls of iridium formed after CO adsorption on Ir-ZSM-5 (Ir-MFI). Mainly Ir+ cations were found on sample activated at 523 K and reduced by CO at the same temperature. With CO they formed Ir+(CO)2 gem-dicarbonyls (2104 and 2033 cm(-1)) that decomposed at 673 K without leaving a measurable fraction of monocarbonyls. The dicarbonyl structure was established by 12CO-13CO coadsortpion experiments. In the presence of CO in the gaseous phase and at ambient temperature the Ir+(CO)2 dicarbonyls were converted into Ir+(CO)3 species (2182, 2099, and 2074 cm(-1)). At 100 K these complexes are able to accommodate a fourth CO molecule thus producing tetracarbonyls (2155, 2145, 2125, and 2105 cm(-1)). The results are explained by the high coordinative unsaturation of the Ir+ cations in the ZSM-5 matrix. This is also the reason for the formation of mixed Ir+(H2O)(CO)2 species after CO-H2O coadsorption (2087 and 2015 cm(-1)). Evacuation of the sample at 673 K, followed by treatment with CO at 523 K, generates Ir2+ cations. With CO these cations form another kind of geminal complex, namely, Ir2+(CO)2 species (2173 and 2129 cm(-1)). Here again, the structure was confirmed by 12CO-13CO coadsortpion experiments. These dicarbonyls are decomposed at 573 K (again without producing monocarbonyls) and are able to accommodate additionally neither CO nor water molecules. The results are explained by the smaller cationic radius of Ir2+ (as compared to Ir+), which is associated with a decrease of the number of ligands required for coordinative saturation.