On the relation between basis set convergence and electron correlation: a critical test for modern ab initio quantum chemistry on a "mindless” data set

The correlation of the only two error sources in the solution of the electronic Schrödinger equation is addressed: the basis set convergence (incompleteness) error (BSIE) and the electron correlation effect. The electron correlation effect and basis set incompleteness error are found to be correlated for all of the molecules in Grimme's "mindless” data set (MB08-165). One can use an extrapolation to the HF or MP2 complete basis set (CBS) limit to see with which type of quantum chemical problem ("simple” and "hard”) the researcher is dealing. The origin of the slow convergence of the partial wave expansion can be the Kato cusp condition for electron-electron coalescence. Such an extrapolation is possible for many large molecular systems and would give the researcher an idea about the expected electron correlation level that would lead to the desired theoretical accuracy. In other words, it is possible to use not only the CBS energy value itself but the speed with which it is reached to get extra information about the molecular system under stud

Fragmentation of benzylpyridinium "thermometer” ions and its effect on the accuracy of internal energy calibration

Electrospray ionization mass spectrometry (ESI-MS) is a powerful analytical method to study biomolecules and noncovalent complexes. The prerequisite for their intact observation is soft ionization. In ESI, the internal energy of ions is primarily influenced by collisional activation in the source. The survival yield method is frequently used to probe the energy deposition in ions during the electrospray process. In the present work, we investigate the fragmentation pathways of para-substituted benzylpyridinium ions, the most widely used "thermometer ions” in the survival yield method. In addition to the C-N bond cleavage, alternative fragmentation channels were found for the compounds studied. We consider these pathways to result from intramolecular rearrangements. The effect of these additional fragments on the accuracy of the internal energy calibration is estimated for both collision-cell and in-source collision-induced dissociation (CID). Altogether, results presented suggest that a correction of the energy scale is necessary for the method based on benzylpyridinium ions to precisely quantify ion internal energie

THE CONCEPT OF THE LINGUISTIC SUPPORT FOR FORCES

The author presents the concept of the linguistic support for forces, which is fundamental for the conceptual construct of the military translation theory. The linguistic support for forces (LSF) is a complex of special measures, tasks, procedures and processes of practical and fundamental nature in the military-political, military-technical and special military fields of the Armed Forces of Ukraine. They are planned and carried out to accomplish intercultural (communicative & mediational), linguo-geographical (informational & analytic), military-terminological (normative & codifying), linguo-pedagogical (didactic & diagnostic) and linguo-research (scholarly) functions that require military-professional level of bilingual philological competence of performers.Keywords: translation studies, military translation (MILT), theory of military translation, linguistic support for forces (LSF).кандидат філологічних наук, професор, Балабін В. В. Концепція лінгвістичного забезпечення військ/ Військовий інститут Київського національного університету імені Тараса Шевченка, Україна, КиївСтаттю присвячено обґрунтуванню основних понять концепції лінгвістичного забезпечення військ, яка є однією із основоположних у теорії військового перекладу. Лінгвістичне забезпечення військ (ЛЗВ) – це комплекс спеціальних заходів, завдань, процедур і процесів прикладного й фундаментального характеру у військово-політичній, військово-технічній та військово-спеціальних сферах діяльності Збройних сил України, що здійснюються з метою реалізації міжкультурної (комунікативно-посередницької), лінгвокраїнознавчої (інформаційно-аналітичної), військово-термінологічної (нормативно-кодифікуючої), лінгвопедагогічної (дидактично-діагностичної) та лінгводослідницької (науково-пошукової) функцій, які потребують військово-професійного рівня філологічної білінгвальної компетенції виконавців.Ключові слова: перекладознавство, військовий переклад, теорія військового перекладу, лінгвістичне забезпечення військ (ЛЗВ

Mixed Approaches to Handle Limitations and Execute Mutation in the Genetic Algorithm for Truss Size, Shape and Topology Optimization

A high-performance genetic algorithm for the optimal synthesis of trusses in discrete search spaces is developed. The main feature of the proposed computational procedure is the possibility of obtaining effective solutions without the violation of any constraint. In general, a varying of cross-sectional areas of bars, coordinates of nodes and topology system is provided. A group of individuals in the population can be accepted for further consideration only if all specified limitations have been fulfilled. Penalties that significantly change an objective function are introduced for other individuals. This mechanism of handling limitations provides for correction of inaccuracies that can introduce penalty functions for satisfying the problem conditions. Both a random change to the entire set of admissible values and a random choice of values among adjacent elements in this set can be performed during the mutation stage. Standard test examples for benchmark mathematical functions and trusses show high efficiency of the considered iterative procedure in terms of solution accuracy

Disentanglement Learning via Topology

We propose TopDis (Topological Disentanglement), a method for learning disentangled representations via adding multi-scale topological loss term. Disentanglement is a crucial property of data representations substantial for the explainability and robustness of deep learning models and a step towards high-level cognition. The state-of-the-art method based on VAE minimizes the total correlation of the joint distribution of latent variables. We take a different perspective on disentanglement by analyzing topological properties of data manifolds. In particular, we optimize the topological similarity for data manifolds traversals. To the best of our knowledge, our paper is the first one to propose a differentiable topological loss for disentanglement. Our experiments have shown that the proposed topological loss improves disentanglement scores such as MIG, FactorVAE score, SAP score and DCI disentanglement score with respect to state-of-the-art results. Our method works in an unsupervised manner, permitting to apply it for problems without labeled factors of variation. Additionally, we show how to use the proposed topological loss to find disentangled directions in a trained GAN

Энергетическое влияние степени гидратации этанола и коэффициента избыточного воздуха (α) на использование смесей этанол-бензина в двигателях с искровым зажиганием

The objective of this study was to evaluate energetically the effect of hydration degree and mixture type (rich mixture α = 0,85 and lean mixture α = 0,15) on the use of ethanol and gasoline mixtures in spark ignition engines. The experiments were carried out in the Propulsion Laboratory of the Faculty of Engineering Sciences of Agrarian University of Havana (AUH). The JACTO model engine used has an effective power of 1,2 kW, speed 580 rpm, combustion chamber volume 34 cm3. Before combustion, the degree of ethanol hydration was determined (80 %; 85 %; 90 %; 95 %). Taking into account the influence of the percentage of purity of ethanol and air excess coefficient (α), when using combustible mixtures, analyses were carried out on the following parameters: air-fuel ratio (ra/f) and fuel-air ratio (rf/a); internal energy of combustion products (Uz); the number of moles of raw materials in the mixture for gasoline engines (M1) and the number of moles of products during combustion (M2). Based on the experimental work performed and the energy analysis of the combustion process, it was shown that the mixture of gasoline E-10-EH-80 % received more air and fuel than ratio necessary to achieve combustion, reaching 11,781 kg (air)/kg (fuel) for α = 0,85 and 15,309 kg (air)/kg (fuel) for α = 1,15. This is due to the fact that this is a mixture with increased moisture, because it contains more oxygen atoms, which impoverishes the mixture, and guarantees the best quality in the combustion process. But rich mixtures (α = 0,85) were the most energy efficient, which is associated with an increase in the octane number, that is, the antiknock ability of the fuel mixture used, which improves the quality of combustion, although it reduces the energy output during an explosion (detonation).Цель этого исследования – энергетически оценить влияние степени гидратации и типа смеси (богатой смеси α = 0,85 и бедной смеси α = 0,15) на использование смесей этанола и бензина в двигателях с искровым зажиганием. Эксперименты проводились в Лаборатории двигателей Факультета технических наук Гаванского аграрного университета (УНАХ). Используемый двигатель модели JACTO имеет эффективную мощность 1,2 кВт. Частота вращения – 580 об./мин, объём камеры сгорания – 34 см3. Перед сжиганием определяли степень гидратации этанола (80 %; 85 %; 90 %; 95 %). С учётом влияния процента чистоты этанола и коэффициента избыточного воздуха (α) при использовании горючих смесей были проведены анализы следующих параметров: соотношение воздух-топливо (св/т) и соотношение топливо-воздух (ст/в); внутренняя энергия продуктов сгорания (Uz); количество молей исходных веществ в смеси для бензиновых двигателей (M1) и количество молей продуктов при сгорании (M2).На основе выполненных экспериментальных работ и энергетического анализа процесса сгорания показано, что в смеси бензина E‑10-EH‑80 % содержалось большее соотношение воздуха и топлива, чем необходимо для достижения сгорания. Это соотношение достигает 11,781 кг (воздуха)/кг (топлива) для α = 0,85 и 15,309 кг (воздуха)/кг (топлива) для α = 1,15. Это связано с тем, что компоненты с повышенным содержанием влаги обедняют смесь и гарантируют лучшее сгорание. При этом богатые смеси (α = 0,85) оказались наиболее энергоэффективны по причине увеличения октанового числа и соответственно улучшения антидетонационных способностей используемой топливной смеси. Однако, с другой стороны, возможно снижение энергетической эффективности при появлении детонационных процессов

Теплотехнические основы создания пароаккумуляторных локомотивов

The article deals with the problems of creating and using of locomotives run on stored thermal resources (steam) and intended for industrial enteerprises. The objectives of their development and introduction are still relevant and consist in implementation of economical and environmentally friendly locomotives for nonpublic access roads.Shunting operations are considered as an independent type of enterprises’ activity that is not related to their main activity. The locomotives of transport workshops used today for this purpose consume diesel fuel, which significantly increases the logistics cost of goods and reduces the final profit.The article considers one of the possible ways to make the thermal energy (steam) traditionally utilised for technological purposes, to perform other work, which from an energy-economic point of view will be done free of charge, since the cost of energy generation is already covered by the cost of products.For internal and access roads of enterprises, a version of a fireless locomotive with a traction force of 90 kN (9 t) has been developed. This machine does not need fuel but uses process  am obtained from stationary boilers of enterprises and accumulated in a high-pressure tank with thermal insulation.The locomotive was created based on the 9P type 0-3-0 tank locomotive, which was common before. The boiler with a furnace was replaced by a steam storage boiler, which is a closed cylindrical tank with a high degree of thermal insulation.The estimated time of operation of the machine on a single charge is 6–8 hours. The maximum estimated mass of the train on a straight section of the track at a speed of 30 km/h and a traction force of 83 kN•t is 3000 tons.The use of this type of locomotive makes it possible to save diesel fuel in the amount of 0,75–1,0 t/day, reduce repair costs by 90 % compared to a diesel locomotive, reduce the cost of maintenance personnel, get the opportunity to use it in enterprises requiring increased explosive and fire safety.An example of calculating the use of six locomotives at an oil refinery is given, which will give an annual saving of 1444 tons of diesel fuel, with a payback period of the locomotive itself of 3,2 years.В статье рассмотрены этапы создания и применения на промышленных предприятиях теплоаккумуляторных (пароаккумуляторных) локомотивов, цели их создания до сих пор актуальны – это разработка и внедрение экономичных и экологически чистых локомотивов для подъездных путей необщего пользования.Выполнение маневровых работ рассматривается как самостоятельный род деятельности предприятий, не связанных с их основной деятельностью. Применяемые сегодня для этой цели локомотивы транспортных цехов предприятий расходуют дизельное топливо, что заметно повышает логистическую стоимость грузов и снижает конечную прибыль.В статье рассмотрено одно из направлений использования тепловой энергии (пара), идущей на технологические цели, которую можно утилизировать для выполнения иной работы, что с энергоэкономической точки зрения будет выполнено бесплатно, так как стоимость получения энергии уже покрыта стоимостью выпускаемой продукции.Специально для предприятий и подъездных путей к ним разработан пароаккумуляторный локомотив с силой тяги в 90 кН (9 т). Он не нуждается в топливе, а работает на технологическом паре, который поступает от стацио-нарных котлов предприятий и аккумулируется в резервуаре высокого давления с теплоизоляцией.Локомотив был спроектирован на базе модели танкпаровоза 9П типа 0-3-0, который использовался раньше. Котёл и топка были заменены котлом с паронакопителем (закрытый цилиндрический резервуар с высокой степенью термоизоляции). Расчётное время работы машины на одной зарядке – 6–8 ч. Максимальная расчётная масса состава на прямом участке пути при скорости 30 км/ч и силе тяге 83 кН•т составляет 3000 т.Применение такого типа локомотива позволяет: экономить дизельное топливо в количестве 0,75–1,0 т/сут, снизить затраты на ремонт на 90 % по сравнению с тепловозом, уменьшить затраты на обслуживающий персонал, получить возможность использования на предприятиях, предъявляющих повышенные требования по взрывои пожаробезопасности..Дан пример расчёта применения шести локомотивов на нефтеперерабатывающем заводе, что даст годовую экономию дизельного топлива 1444 т, при сроке окупаемости самого локомотива 3,2 года

What Happens to Hydrophobic Interactions during Transfer from the Solution to the Gas Phase? The Case of Electrospray-Based Soft Ionization Methods

The disappearance of the hydrophobic effect in the gas phase due to the absence of an aqueous surrounding raises a long-standing question: can noncovalent complexes that are exclusively bound by hydrophobic interactions in solution be preserved in the gas phase? Some reports of successful detection by mass spectrometry of complexes largely stabilized by hydrophobic effect are questionable by the presence of electrostatic forces that hold them together in the gas phase. Here, we report on the MS-based analysis of model supramolecular complexes with a purely hydrophobic association in solution, β-cyclodextrin, and synthetic adamantyl-containing ligands with several binding sites. The stability of these complexes in the gas phase is investigated by quantum chemical methods (DFT-M06). Compared with the free interaction partners, the inclusion complex between β-cyclodextrin and adamantyl-containing ligand is shown to be stabilized in the gas phase by ΔG = 9.6kcal mol-1. The host-guest association is mainly enthalpy-driven due to strong dispersion interactions caused by a large nonpolar interface and a high steric complementarity of the binding partners. Interference from other types of noncovalent binding forces is virtually absent. The complexes are successfully detected via electrospray ionization mass spectrometry, although a high dissociation yield is also observed. We attribute this pronounced dissociation of the complexes to the collisional activation of ions in the atmospheric interface of mass spectrometer. The comparison of several electrospray-based ionization methods reveals that cold spray ionization provides the softest ion generation conditions for these complexe

Learning Topology-Preserving Data Representations

We propose a method for learning topology-preserving data representations (dimensionality reduction). The method aims to provide topological similarity between the data manifold and its latent representation via enforcing the similarity in topological features (clusters, loops, 2D voids, etc.) and their localization. The core of the method is the minimization of the Representation Topology Divergence (RTD) between original high-dimensional data and low-dimensional representation in latent space. RTD minimization provides closeness in topological features with strong theoretical guarantees. We develop a scheme for RTD differentiation and apply it as a loss term for the autoencoder. The proposed method "RTD-AE" better preserves the global structure and topology of the data manifold than state-of-the-art competitors as measured by linear correlation, triplet distance ranking accuracy, and Wasserstein distance between persistence barcodes

Insight into the redox partner interaction mechanism in cytochrome P450BM-3 using molecular dynamics simulations

Flavocytochrome P450BM-3 is a soluble bacterial reductase composed of two flavin (FAD/FMN) and one HEME domains. In this article, we have performed molecular dynamics simulations on both the isolated FMN and HEME domains and their crystallographic complex, with the aim to study their binding modes and to garner insight into the interdomain electron transfer (ET) mechanism. The results evidenced an interdomain conformational rearrangement that reduces the average distance between the FMN and HEME cofactors from 1.81 nm, in the crystal structure, to an average value of 1.41 ± 0.09 nm along the simulation. This modification is in agreement with previously proposed hypotheses suggesting that the crystallographic FMN/HEME complex is not in the optimal arrangement for favorable ET rate under physiological conditions. The calculation of the transfer rate along the simulation, using the Pathways Path method, demonstrated the occurrence of seven ET pathways between the two redox centers, with three of them providing ET rates (KET ) comparable with the experimental one. The sampled ET pathways comprise the amino acids N319, L322, F390, K391, P392, F393, A399, C400, and Q403 of the HEME domain and M490 of the FMN domain. The values of KET closer to the experiment were found along the pathways FMN(C7) → F390 → K391 → P392 → HEME(Fe) and FMN(C8) → M490 → F393 → HEME(Fe). Finally, the analysis of the collective modes of the protein complex evidences a clear correlation of the first two essential modes with the activation of the most effective ET pathways along the trajectory. © 2013 Wiley Periodicals, Inc. Biopolymers 101: 197-209, 2014