Ab Initio Kinetic Modelling in Radical Polymerization: A Paradigm Shift in Reaction Kinetic Analysis

2006 ◽  
Vol 59 (10) ◽  
pp. 712 ◽  
Author(s):  
Michelle L. Coote ◽  
Christopher Barner-Kowollik
Keyword(s):  
Kinetic Model ◽  
Ab Initio ◽  
Kinetic Modelling ◽  
Raft Polymerization ◽  
Reaction Scheme ◽  
Rate Coefficients ◽  
Macroscopic Properties ◽  
Potential Applications ◽  
The Individual ◽  
High Level

We describe a new rationale to kinetic modelling in which adjustable parameters are avoided through the use of quantum chemistry. This new approach reverses the standard modelling approach in which, having first assumed a kinetic model, it is then fitted to the experimentally determined values of the macroscopic properties (rates, compositions, molecular weight distributions, and so forth) so as to estimate the rate coefficients of the individual reactions. Instead, one still assumes a reaction scheme, but then calculates the rates of the individual reactions using high-level ab initio calculations, and in this way a kinetic model is built that can be used to predict the macroscopic properties of the process from first principles. These can then be compared directly with experiment (for benchmarking purposes) and subsequently be employed to predict the outcome of new chemical processes. In here we illustrate the ab initio modelling technique, using a recent study of initialization in RAFT polymerization as a case study. We also discuss its advantages and possible problems, and highlight some of its potential applications in the radical polymer field.

How Well Can Theory Predict Addition - Fragmentation Equilibrium Constants in RAFT Polymerization?

2009 ◽  
Vol 62 (11) ◽  
pp. 1479 ◽  
Author(s):  
Ching Yeh Lin ◽  
Michelle L. Coote
Keyword(s):  
Ab Initio ◽  
Chain Length ◽  
Methyl Acrylate ◽  
Raft Polymerization ◽  
Equilibrium Constants ◽  
Molecular Orbital Calculations ◽  
Related System ◽  
Order Of Magnitude ◽  
Good Order ◽  
High Level

High level ab initio molecular orbital calculations are used to study the addition–fragmentation equilibrium constants of S-S’-bis(methyl-2-propionate)-trithiocarbonate mediated polymerization of methyl acrylate in toluene at –30°C. The results, which show strong solvent and chain length effects, are in good order of magnitude agreement with recent experimental results for a closely related system.

Towards a New Approach to Cross-Cultural Distinctiveness and Typicality of Human Faces: The Cross-Group Typicality/Distinctiveness Metric

2018 ◽  
Author(s):  
Karel Kleisner ◽  
Šimon Pokorný ◽  
Selahattin Adil Saribay
Keyword(s):  
Cross Cultural ◽  
Facial Appearance ◽  
Alternative Measure ◽  
Home Culture ◽  
Facial Stimuli ◽  
The Two Cultures ◽  
Potential Applications ◽  
The Individual ◽  
Human Faces ◽  
Ingroup Outgroup

In present research, we took advantage of geometric morphometrics to propose a data-driven method for estimating the individual degree of facial typicality/distinctiveness for cross-cultural (and other cross-group) comparisons. Looking like a stranger in one’s home culture may be somewhat stressful. The same facial appearance, however, might become advantageous within an outgroup population. To address this fit between facial appearance and cultural setting, we propose a simple measure of distinctiveness/typicality based on position of an individual along the axis connecting the facial averages of two populations under comparison. The more distant a face is from its ingroup population mean towards the outgroup mean the more distinct it is (vis-à-vis the ingroup) and the more it resembles the outgroup standards. We compared this new measure with an alternative measure based on distance from outgroup mean. The new measure showed stronger association with rated facial distinctiveness than distance from outgroup mean. Subsequently, we manipulated facial stimuli to reflect different levels of ingroup-outgroup distinctiveness and tested them in one of the target cultures. Perceivers were able to successfully distinguish outgroup from ingroup faces in a two-alternative forced-choice task. There was also some evidence that this task was harder when the two faces were closer along the axis connecting the facial averages from the two cultures. Future directions and potential applications of our proposed approach are discussed.

Territorial Distribution of Alcohol and Drug Addictions Mortality Concerning Regional Disparities in the Slovak Republic from Year 1996 to Year 2015

2020 ◽  
Keyword(s):  
Mortality Rate ◽  
Slovak Republic ◽  
Regional Disparities ◽  
Point Of View ◽  
Extreme Position ◽  
Data Set ◽  
Female Sex ◽  
Male Sex ◽  
The Individual ◽  
High Level

BACKGROUND: This paper deals with territorial distribution of the alcohol and drug addictions mortality at a level of the districts of the Slovak Republic. AIM: The aim of the paper is to explore the relations within the administrative territorial division of the Slovak Republic, that is, between the individual districts and hence, to reveal possibly hidden relation in alcohol and drug mortality. METHODS: The analysis is divided and executed into the two fragments – one belongs to the female sex, the other one belongs to the male sex. The standardised mortality rate is computed according to a sequence of the mathematical relations. The Euclidean distance is employed to compute the similarity within each pair of a whole data set. The cluster analysis examines is performed. The clusters are created by means of the mutual distances of the districts. The data is collected from the database of the Statistical Office of the Slovak Republic for all the districts of the Slovak Republic. The covered time span begins in the year 1996 and ends in the year 2015. RESULTS: The most substantial point is that the Slovak Republic possesses the regional disparities in a field of mortality expressed by the standardised mortality rate computed particularly for the diagnoses assigned to the alcohol and drug addictions at a considerably high level. However, the female sex and the male sex have the different outcome. The Bratislava III District keeps absolutely the most extreme position. It forms an own cluster for the both sexes too. The Topoľčany District bears a similar extreme position from a point of view of the male sex. All the Bratislava districts keep their mutual notable dissimilarity. Contrariwise, evaluation of a development of the regional disparities among the districts looks like notably heterogeneously. CONCLUSIONS: There are considerable regional discrepancies throughout the districts of the Slovak Republic. Hence, it is necessary to create a common platform how to proceed with the solution of this issue.

Quantitative indicators of air traffic controllers’ attitude to the danger of errors

2020 ◽  
pp. 68-78
Author(s):  
O. M. Reva ◽  
V. V. Kamyshin ◽  
S. P. Borsuk ◽  
V. A. Shulhin ◽  
A. V. Nevynitsyn
Keyword(s):  
Human Factor ◽  
Differential Method ◽  
Air Traffic ◽  
Professional Activity ◽  
Aviation Accidents ◽  
Air Traffic Controllers ◽  
The Difference ◽  
Level Of Significance ◽  
The Individual ◽  
High Level

The negative and persistent impact of the human factor on the statistics of aviation accidents and serious incidents makes proactive studies of the attitude of “front line” aviation operators (air traffic controllers, flight crewmembers) to dangerous actions or professional conditions as a key component of the current paradigm of ICAO safety concept. This “attitude” is determined through the indicators of the influence of the human factor on decision-making, which also include the systems of preferences of air traffic controllers on the indicators and characteristics of professional activity, illustrating both the individual perception of potential risks and dangers, and the peculiarities of generalized group thinking that have developed in a particular society. Preference systems are an ordered (ranked) series of n = 21 errors: from the most dangerous to the least dangerous and characterize only the danger preference of one error over another. The degree of this preference is determined only by the difference in the ranks of the errors and does not answer the question of how much time one error is more dangerous in relation to another. The differential method for identifying the comparative danger of errors, as well as the multistep technology for identifying and filtering out marginal opinions were applied. From the initial sample of m = 37 professional air traffic controllers, two subgroups mB=20 and mG=7 people were identified with statisti-cally significant at a high level of significance within the group consistency of opinions a = 1%. Nonpara-metric optimization of the corresponding group preference systems resulted in Kemeny’s medians, in which the related (middle) ranks were missing. Based on these medians, weighted coefficients of error hazards were determined by the mathematical prioritization method. It is substantiated that with the ac-cepted accuracy of calculations, the results obtained at the second iteration of this method are more ac-ceptable. The values of the error hazard coefficients, together with their ranks established in the preference systems, allow a more complete quantitative and qualitative analysis of the attitude of both individual air traffic controllers and their professional groups to hazardous actions or conditions.

scholarly journals Automatic Labeled Dialogue Generation for Nursing Record Systems

2020 ◽  
Vol 10 (3) ◽  
pp. 62
Author(s):  
Tittaya Mairittha ◽  
Nattaya Mairittha ◽  
Sozo Inoue
Keyword(s):  
Data Augmentation ◽  
Short Term Memory ◽  
Generative Models ◽  
Abstract Knowledge ◽  
Augmentation Techniques ◽  
Nursing Record ◽  
Long Short Term Memory ◽  
The Individual ◽  
High Level ◽  
Embedding Methods

The integration of digital voice assistants in nursing residences is becoming increasingly important to facilitate nursing productivity with documentation. A key idea behind this system is training natural language understanding (NLU) modules that enable the machine to classify the purpose of the user utterance (intent) and extract pieces of valuable information present in the utterance (entity). One of the main obstacles when creating robust NLU is the lack of sufficient labeled data, which generally relies on human labeling. This process is cost-intensive and time-consuming, particularly in the high-level nursing care domain, which requires abstract knowledge. In this paper, we propose an automatic dialogue labeling framework of NLU tasks, specifically for nursing record systems. First, we apply data augmentation techniques to create a collection of variant sample utterances. The individual evaluation result strongly shows a stratification rate, with regard to both fluency and accuracy in utterances. We also investigate the possibility of applying deep generative models for our augmented dataset. The preliminary character-based model based on long short-term memory (LSTM) obtains an accuracy of 90% and generates various reasonable texts with BLEU scores of 0.76. Secondly, we introduce an idea for intent and entity labeling by using feature embeddings and semantic similarity-based clustering. We also empirically evaluate different embedding methods for learning good representations that are most suitable to use with our data and clustering tasks. Experimental results show that fastText embeddings produce strong performances both for intent labeling and on entity labeling, which achieves an accuracy level of 0.79 and 0.78 f1-scores and 0.67 and 0.61 silhouette scores, respectively.

scholarly journals Opportunities and Challenges of Green-Lean: An Integrated System for Sustainable Construction

2020 ◽  
Vol 12 (11) ◽  
pp. 4460 ◽  
Author(s):  
Mohammadsoroush Tafazzoli ◽  
Ehsan Mousavi ◽  
Sharareh Kermanshachi
Keyword(s):  
Cost Savings ◽  
Integrated Approach ◽  
Integrated System ◽  
Waste Minimization ◽  
Sustainable Construction ◽  
Future Research ◽  
Safety Improvement ◽  
The Individual ◽  
High Level ◽  
Industry Professionals

Although the two concepts of lean and sustainable construction have been developed due to different incentives, and they do not pursue the same exact goals, there exists considerable commonality between them. This paper discusses the potentials for integrating the two approaches and their practices and how the resulting synergy from combining the two methods can potentially lead to higher levels of fulfilling the individual goals of each of them. Some limitations and challenges to implementing the integrated approach are also discussed. Based on a comprehensive review of existing papers related to sustainable and lean construction topics, the commonality between the two approaches is discussed and grouped in five categories of (1) cost savings, (2) waste minimization, (3) Jobsite safety improvement, (4) reduced energy consumption, and (5) customers’ satisfaction improvement. The challenges of this integration are similarly identified and discussed in the four main categories of (1) additional initial costs to the project, (2) difficulty of providing specialized expertise, (3) contractors’ unwillingness to adopt the additional requirements, and (4) challenges to establish a high level of teamwork. Industry professionals were then interviewed to rank the elements in each of the two categories of opportunities and challenges. The results of the study highlight how future research can pursue the development of a new Green-Lean approach by investing in the communalities and meeting the challenges of this integration.

Rotational de-excitations of C3H+ (1Σ+) by collision with He: new ab initio potential energy surface and scattering calculations

2020 ◽  
Vol 494 (4) ◽  
pp. 5675-5681 ◽  
Author(s):  
Sanchit Chhabra ◽  
T J Dhilip Kumar
Keyword(s):  
Potential Energy ◽  
Potential Energy Surface ◽  
Ab Initio ◽  
Cross Sections ◽  
Energy Surface ◽  
Molecular Ions ◽  
Basis Set ◽  
Rate Coefficients ◽  
Close Coupling ◽  
Collisional Rate Coefficients

ABSTRACT Molecular ions play an important role in the astrochemistry of interstellar and circumstellar media. C3H+ has been identified in the interstellar medium recently. A new potential energy surface of the C3H+–He van der Waals complex is computed using the ab initio explicitly correlated coupled cluster with the single, double and perturbative triple excitation [CCSD(T)-F12] method and the augmented correlation consistent polarized valence triple zeta (aug-cc-pVTZ) basis set. The potential presents a well of 174.6 cm−1 in linear geometry towards the H end. Calculations of pure rotational excitation cross-sections of C3H+ by He are carried out using the exact quantum mechanical close-coupling approach. Cross-sections for transitions among the rotational levels of C3H+ are computed for energies up to 600 cm−1. The cross-sections are used to obtain the collisional rate coefficients for temperatures T ≤ 100 K. Along with laboratory experiments, the results obtained in this work may be very useful for astrophysical applications to understand hydrocarbon chemistry.

Configurational Assignment and Conformational Study of Methylglyoxal Bisdimethylhydrazones Derived from the 2-Ethoxypropenal Precursor

2006 ◽  
Vol 59 (3) ◽  
pp. 211 ◽  
Author(s):  
Leonid B. Krivdin ◽  
Lyudmila I. Larina ◽  
Kirill A. Chernyshev ◽  
Natalia A. Keiko
Keyword(s):  
Ab Initio Calculations ◽  
Ab Initio ◽  
Experimental Measurements ◽  
Conformational Study ◽  
Lone Pairs ◽  
Configurational Assignment ◽  
Out Of Plane ◽  
High Level

A configurational assignment of the isomeric methylglyoxal bisdimethylhydrazones derived from the 2-ethoxypropenal precursor has been performed based on experimental measurements and high-level ab initio calculations of 1J(C,C) and 1J(C,H) couplings. The results reveal the marked stereochemical dependence upon the orientation of the lone pairs of both nitrogen atoms in different isomers. Methylglyoxal bisdimethylhydrazone is shown to exist in a mixture of the EE and ZE isomers (ca. 75:25), both of which adopt predominant s-trans conformations with minor (up to 8°) out-of-plane deviations.

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