Development and Benchmarking of Novel Electronic Structure Methods based on the Algebraic Diagrammatic Construction and Unitary Coupled Cluster Schemes

During the last three decades, the field of theoretical and computational chemistry has evolved rapidly, promoted by the increasing availability of computational power inherent in modern CPUs and cluster structures. This development has expressed itself in a particular manner in the formulation of modern state-of-the-art electronic structure methods in the frameworks of, for instance, the Algebraic Diagrammatic Construction scheme or Coupled Cluster. Application of these methods to the calculation of molecular excitation energies and properties that describe the most fundamental processes of light-matter interaction, has been established as a profound and reliable tool for experimentalists within chemistry and molecular sciences. This work, which is spilt into three main parts, presents the implementation as well as benchmarking of novel electronic structure methods for the Algebraic Diagrammatic Construction scheme (ADC) as well as Unitary Coupled Cluster (UCC). In the first part, an implementation and benchmark study for the calculation doubly-ionized as well as double electronically-attached states for ADC, termed DIP-ADC and DEA-ADC, respectively, up to third order is presented. The implementation was executed in the Q-Chem program package, benchmark studies included the comparison of states to Full CI data for DIP as well as EOMDIP-CCSD and EOMDEA-CCSD. For both schemes, the third-order methods DIP-ADC(3) as well as DEA-ADC(3) proved to produce results which are in a remarkable good agreement to the corresponding EOM-CCSD method. As for the second part, a benchmark study on core excitation energies in the framework of Unitary Coupled Cluster was presented. To this end, the Core-valence separation approximation was applied to the second-and third-order UCC schemes for electron excitations. It was shown that CVS-UCC is very suitable in the computation of X-ray spectra, similar to CVS-ADC, which has been studied before by Wenzel et al. and that it provides reliable data for the description and simulation of energetically high-lying core excitations. The last part of this work features an implementation of an automated code generator for Unitary Coupled Cluster as it was realized by Leitner et al. for the computation of electronically excited states on a ADC(4) level. Working equations for a UCC3-x scheme (in similarity to UCC2-x with an extended description of the doubles/doubles block of the secular matrix) as well as a full UCC4 for the calculation of electronically-excited states and properties are presented, together with an improved ground-state description, termed UCC4+5[s,t] that includes fifth-order terms. At the end of this work, all results for the three presented topics are summarized in detail, accompanied by a short outlook of what could include future work and development

"suMus," a novel digital system for arm movement metrics and muscle energy expenditure

OBJECTIVE: In the field of non-treatable muscular dystrophies, promising new gene and cell therapies are being developed and are entering clinical trials. Objective assessment of therapeutic effects on motor function is mandatory for economical and ethical reasons. Main shortcomings of existing measurements are discontinuous data collection in artificial settings as well as a major focus on walking, neglecting the importance of hand and arm movements for patients' independence. We aimed to create a digital tool to measure muscle function with an emphasis on upper limb motility. METHODS: suMus provides a custom-made App running on smartwatches. Movement data are sent to the backend of a suMus web-based platform, from which they can be extracted as CSV data. Fifty patients with neuromuscular diseases assessed the pool of suMus activities in a first orientation phase. suMus performance was hence validated in four upper extremity exercises based on the feedback of the orientation phase. We monitored the arm metrics in a cohort of healthy volunteers using the suMus application, while completing each exercise at low frequency in a metabolic chamber. Collected movement data encompassed average acceleration, rotation rate as well as activity counts. Spearman rank tests correlated movement data with energy expenditure from the metabolic chamber. RESULTS: Our novel application "suMus," sum of muscle activity, collects muscle movement data plus Patient-Related-Outcome-Measures, sends real-time feedback to patients and caregivers and provides, while ensuring data protection, a long-term follow-up of disease course. The application was well received from the patients during the orientation phase. In our pilot study, energy expenditure did not differ between overnight fasted and non-fasted participants. Acceleration ranged from 1.7 ± 0.7 to 3.2 ± 0.5 m/sec(2) with rotation rates between 0.9 ± 0.5 and 2.0 ± 3.4 rad/sec. Acceleration and rotation rate as well as derived activity counts correlated with energy expenditure values measured in the metabolic chamber for one exercise (r = 0.58, p < 0.03). CONCLUSION: In the analysis of slow frequency movements of upper extremities, the integration of the suMus application with smartwatch sensors characterized motion parameters, thus supporting a use in clinical trial outcome measures. Alternative methodologies need to complement indirect calorimetry in validating accelerometer-derived energy expenditure data

О некоторых мерах государственной поддержки субъектов сельскохозяйственной деятельности в рамках интеграционных процессов

Материалы IX Междунар. науч.-практ. конф., Гомель, 26-27 ноября 2015

Dynamics on Multiple Potential Energy Surfaces: Quantitative Studies of Elementary Processes Relevant to Hypersonics

The determination of thermal and vibrational relaxation rates of triatomic systems suitable for application in hypersonic model calculations is discussed. For this, potential energy surfaces for ground and electronically excited state species need to be computed and represented with high accuracy and quasiclassical or quantum nuclear dynamics simulations provide the basis for determining the relevant rates. These include thermal reaction rates, state-to-state cross-sections, or vibrational relaxation rates. For exemplary systems - [NNO], [NOO], and [CNO] - all individual steps are described and a literature overview for them is provided. Finally, as some of these quantities involve considerable computational expense, for the example of state-to-state cross sections the construction of an efficient model based on neural networks is discussed. All such data is required and being used in more coarse-grained computational fluid dynamics simulations.Comment: Review article, 46 pages, 8 figure

ARTEFACTS: How do we want to deal with the future of our one and only planet?

The European Commission’s Science and Knowledge Service, the Joint Research Centre (JRC), decided to try working hand-in-hand with leading European science centres and museums. Behind this decision was the idea that the JRC could better support EU Institutions in engaging with the European public. The fact that European Union policies are firmly based on scientific evidence is a strong message which the JRC is uniquely able to illustrate. Such a collaboration would not only provide a platform to explain the benefits of EU policies to our daily lives but also provide an opportunity for European citizens to engage by taking a more active part in the EU policy making process for the future. A PILOT PROGRAMME To test the idea, the JRC launched an experimental programme to work with science museums: a perfect partner for three compelling reasons. Firstly, they attract a large and growing number of visitors. Leading science museums in Europe have typically 500 000 visitors per year. Furthermore, they are based in large European cities and attract local visitors as well as tourists from across Europe and beyond. The second reason for working with museums is that they have mastered the art of how to communicate key elements of sophisticated arguments across to the public and making complex topics of public interest readily accessible. That is a high-value added skill and a crucial part of the valorisation of public-funded research, never to be underestimated. Finally museums are, at present, undergoing something of a renaissance. Museums today are vibrant environments offering new techniques and technologies to both inform and entertain, and attract visitors of all demographics.JRC.H.2-Knowledge Management Methodologies, Communities and Disseminatio

Sleep supports selective retention of associative memories based on relevance for future utilization

Contains fulltext : 102880.pdf (publisher's version ) (Open Access)An outstanding question is whether memory consolidation occurs passively or involves active processes that selectively stabilize memories based on future utility. Here, we differentially modulated the expected future relevance of two sets of picture-location associations after learning. Participants first studied two sets of picture-location associations. After a baseline memory test, they were instructed that only one set of associations would be retested after a 14-hour delay. For half of the participants, this test-retest delay contained a night of sleep; for the other half the delay included a normal working day. At retest, participants were re-instructed and against their expectations tested on both sets of associations. Our results show that post-learning instruction about subsequent relevance selectively improves memory retention for specific associative memories. This effect was sleep-dependent; it was present only in the group of subjects for which the test-retest delay contained sleep. Moreover, time spent asleep for participants in this sleep group correlated with retention of relevant but not irrelevant associations; participants who slept longer forgot fewer associations from the relevant category. In contrast, participants that did not sleep forgot more relevant than irrelevant associations across the test-retest delay. In summary, our results indicate that it is possible to modulate the retention of selected memories after learning with simple verbal instructions on their future relevance. The finding that this effect depends on sleep demonstrates this state's active role in memory consolidation and may have utility for educational settings.6 p

Mean performance for the WAKE and SLEEP group.

<p> <i>Performance is listed as the number of correct responses (maximum  = 60) with the Standard Error of the Mean in brackets.</i></p