The stability of biradicaloid versus closed-shell [E(μ-XR)]2 (E = P, As; X = N, P, As) rings. Does aromaticity play a role?

2016 ◽  
Vol 18 (17) ◽  
pp. 11879-11884 ◽  
Author(s):  
Rafael Grande-Aztatzi ◽  
Jose M. Mercero ◽  
Jesus M. Ugalde
Keyword(s):  
Ab Initio ◽  
Closed Shell ◽  
The Stability ◽  
High Level

High-level CASSCF calculations, supplemented with MCQDPT ab initio calculations, demonstrate that the [E(μ-XH)]2 (E = P, As; X = N, P, As) compounds possess one planar and one butterfly-like isomers.

The Distal Effect of N-Electron-withdrawing Groups on the Stability of Peptide Carbon Radicals

2011 ◽  
Vol 64 (4) ◽  
pp. 403 ◽  
Author(s):  
Junming Ho ◽  
Michelle L. Coote ◽  
Christopher J. Easton
Keyword(s):  
Hydrogen Bonding ◽  
Ab Initio ◽  
Radical Formation ◽  
Ab Initio Methods ◽  
Amide Nitrogen ◽  
Amide Carbonyl ◽  
Carbon Radicals ◽  
The Stability ◽  
High Level ◽  
Calculated Activation

The effect of electron-withdrawing substituents, hydrogen bonding and protonation at amide nitrogen on the stability of radicals formed by loss of either a distal C–H adjacent to the amide carbonyl or one proximal to the amide nitrogen for a series of acetamides and diketopiperazines has been studied via high-level ab initio methods. These studies show that the effect is to destabilize the radicals formed by abstraction of the proximal hydrogens, typically by 10–20 kJ mol–1, and stabilize the distal radicals typically by 5–10 kJ mol–1, but only if the distal radicals are polarized by another dative substituent. The different radical stabilities are not directly mirrored in calculated activation energies or experimental rates of radical formation in bromination reactions, because there is significant charge development in these reaction transition states.

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.

Radiation Effects on Hollandite Ceramics developed for Radioactive Cesium Immobilization

2003 ◽  
Vol 792 ◽  
Author(s):  
V. Aubin ◽  
D. Caurant ◽  
D. Gourier ◽  
N. Baffier ◽  
S. Esnouf ◽  
...  
Keyword(s):  
Radiation Effects ◽  
Liquid Waste ◽  
Fission Products ◽  
Radioactive Cesium ◽  
Radioactive Liquid Waste ◽  
Epr Spectrum ◽  
Paramagnetic Resonance ◽  
Γ Radiation ◽  
The Stability ◽  
High Level

ABSTRACTProgress on separating the long-lived fission products from the high level radioactive liquid waste (HLW) has led to the development of specific host matrices, notably for the immobilization of cesium. Hollandite (nominally BaAl2Ti6O16), one of the main phases constituting Synroc, receives renewed interest as specific Cs-host wasteform. The radioactive cesium isotopes consist of short-lived Cs and Cs of high activities and Cs with long lifetime, all decaying according to Cs+→Ba2++e- (β) + γ. Therefore, Cs-host forms must be both heat and (β,γ)-radiation resistant. The purpose of this study is to estimate the stability of single phase hollandite under external β and γ radiation, simulating the decay of Cs. A hollandite ceramic of simple composition (Ba1.16Al2.32Ti5.68O16) was essentially irradiated by 1 and 2.5 MeV electrons with different fluences to simulate the β particles emitted by cesium. The generation of point defects was then followed by Electron Paramagnetic Resonance (EPR). All these electron irradiations generated defects of the same nature (oxygen centers and Ti3+ ions) but in different proportions varying with electron energy and fluence. The annealing of irradiated samples lead to the disappearance of the latter defects but gave rise to two other types of defects (aggregates of light elements and titanyl ions). It is necessary to heat at relatively high temperature (T=800°C) to recover an EPR spectrum similar to that of the pristine material. The stability of hollandite phase under radioactive cesium irradiation during the waste storage is discussed.

scholarly journals Density Functional Theory and Complete Basis Set Ab Initio Computational Study of Five-, Six-, Seven- and Eight-hydrogen Coordinated Carbon Cations

1999 ◽  
Vol 23 (8) ◽  
pp. 502-503
Author(s):  
Branko S. Jursic
Keyword(s):  
Density Functional Theory ◽  
Ab Initio ◽  
Density Functional ◽  
Computational Study ◽  
Basis Set ◽  
Functional Theory ◽  
Complete Basis ◽  
Complete Basis Set ◽  
High Level

High level ab initio and density functional theory studies are performed on highly protonated methane species.

scholarly journals Computing the Exact Number of Similarity Classes in the Longest Edge Bisection of Tetrahedra

Mathematics ◽  
2021 ◽  
Vol 9 (12) ◽  
pp. 1447
Author(s):  
Jose P. Suárez ◽  
Agustín Trujillo ◽  
Tania Moreno
Keyword(s):  
Data Structure ◽  
Stability Condition ◽  
Open Problem ◽  
Integer Arithmetic ◽  
Exact Number ◽  
Similarity Class ◽  
The Stability ◽  
High Level ◽  
The Cost

Showing whether the longest-edge (LE) bisection of tetrahedra meshes degenerates the stability condition or not is still an open problem. Some reasons, in part, are due to the cost for achieving the computation of similarity classes of millions of tetrahedra. We prove the existence of tetrahedra where the LE bisection introduces, at most, 37 similarity classes. This family of new tetrahedra was roughly pointed out by Adler in 1983. However, as far as we know, there has been no evidence confirming its existence. We also introduce a new data structure and algorithm for computing the number of similarity tetrahedral classes based on integer arithmetic, storing only the square of edges. The algorithm lets us perform compact and efficient high-level similarity class computations with a cost that is only dependent on the number of similarity classes.

Polaronic and Bipolaronic Enhancement of Second Hyperpolarizabilities in Dithienyl Polyenes from Ab Initio Quantum Methods

1999 ◽  
Vol 597 ◽  
Author(s):  
Steven Trohalaki ◽  
Robert J. Zellmer ◽  
Ruth Pachter
Keyword(s):  
Ab Initio ◽  
Density Functional ◽  
Valence Bond ◽  
Closed Shell ◽  
Functional Theory ◽  
Molecular Conformations ◽  
Hartree Fock ◽  
Molecular Charge ◽  
Field Methodology ◽  
Moller Plesset

AbstractSpangler and He [1,2] have shown that dithienyl polyenes form extremely stable bipolaronic dications when oxidatively doped in solution. Previous theoretical studies applied empirical methods to predict bipolaronic enhancement of hyperpolarizabilities for simple polyenes [3,4]. Here, we employ density functional theory to optimize the gas-phase molecular conformations of neutral, cationic, and dicationic forms of a series of dithienyl polyenes, where the number of ethene units, N, is varied from 1–5. Ab initio Hartree-Fock, generalized valence bond, configuration interaction, and Møller-Plesset calculations demonstrate that the dications are farily well described with a closed shell and therefore have little biradicaloid character. Second hyperpolarizabilities, γ, are subsequently calculated using ab initio Hartree-Fock theory and a finite field methodology. As expected, γ increases with the number of ethene units for a given molecular charge. The cations also show the largest increase in γ with N. For a given value of N, the cations display the largest γ values. However, if we treat the dication as a triplet, which might be present in solution, then it displays the largest γ.

Features of pubertal patients with schizophrenia neurocognitive profile

2017 ◽  
Vol 41 (S1) ◽  
pp. S430-S431
Author(s):  
Y. Barylnik ◽  
S. Pakhomova ◽  
D. Samoylova ◽  
J. Abrosimova ◽  
E. Kolesnichenko ◽  
...  
Keyword(s):  
Stability Index ◽  
Neurocognitive Disorders ◽  
Motor Speed ◽  
Structuring Element ◽  
Test Part ◽  
Psychic Disorders ◽  
Competing Interest ◽  
Neurocognitive Profile ◽  
The Stability ◽  
High Level

Identifying the patterns of neurocognitive disorders in pubertal schizophrenia is actual.MethodsBenton Test of visual retention, methods of forward and reverse bills, Bourdon correction sample, Wechsler's subtests (subtest 11 – “Encryption”, subtest 12 – “Labyrinths” 1, 2, 3, 4, 5), Trail Creating a Test Part A.ResultsAll patients were divided into 3 groups. The first group (schizophrenia) and second group (other psychic disorders) showed the worst results than healthy subjects. Qualitative analysis of the “Benton Test” results showed similar variations of difficulty and types of errors in the subjects of the first and second groups – ignoring the number of the figure sides, as well as difficulties in the structuring element of the image corners. The “Methods of forward and reverse bills” demonstrated the fatigue and attention instability. “Bourdon test” showed a high level of the stability index (K = 0.09). Wechsler's subtest “Encryption B” obtained poor results, indicating a pathological decrease in visual-motor speed. During the subtest “Labyrinths 1, 2, 3, 4, 5” the subjects of first and second groups exceeded the allowable time limit, but the first group of schizophrenia patients allowed more blunders during pubertal study (ignored the walls of the maze, torn pencil despite the given instructions). The test groups 1 and 2 while passing “Trail Creating a Test Part A” have shown good results – job data did not cause difficulties and carried out in accordance with the specified instructions.ConclusionsNeurocognitive disorders allow to confirm the presence of morphological and functional brain changes when endogenous mental illness occurs.Disclosure of interestThe authors have not supplied their declaration of competing interest.

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