Search results for "Calculation"

Weakly interacting dark matter in walking technicolor theories

2010

Several lines of evidence support the existence of the dark matter in the Universe. In the light of the present observations the particle dark matter, and in particular the WIMP scenario is a very promising alternative to solve the dark matter problem. In this context recent minimal walking techicolor model motivated dark matter models have been studied. The minimal walking techinicolor and the minimal extension of it, which can successfully provide a dynamical origin for the electroweak symmetry breaking as well as the unification of the standard model coupling constants, gives rise to natural dark matter candidates such as fourth family heavy neutrinos and SU(2) adjoint matter. A general …

Hydrogenation of but-2-yne-1,4-diol on a palladium cluster: a computational study

2013

Airy-function approach to binary black hole merger waveforms: The fold-caustic diffraction model

2022

From numerical simulations of the Einstein equations, and also from gravitational wave observations, the gravitational wave signal from a binary black hole merger is seen to be simple and to possess certain universal features. The simplicity is somewhat surprising given that non-linearities of general relativity are thought to play an important role at the merger. The universal features include an increasing amplitude as we approach the merger, where transition from an oscillatory to a damped regime occurs in a pattern apparently oblivious to the initial conditions. We propose an Airy-function pattern to model the binary black hole (BBH) merger waveform, focusing on accounting for its simpl…

Recent Developments in the Chiral Brønsted Acid-catalyzed Allylboration Reaction with Polyfunctionalized Substrates

2016

Asymmetric allylboration has played a central role in organic synthesis ever since the pioneering work by Hoffman and Brown, having found applications in the total synthesis of many natural products. A new dawn for this 40 year-old reaction occurred with the beginning of the new century when the first catalytic asymmetric methods came into play. In less than one decade, several methodologies, able to achieve the desired homoallylic alcohols with ee ranges in the high 90s, were developed. Among them, in the present account, we will disclose our contribution to the development of the chiral binolphosphoric-derived BrOnsted acid-catalyzed allylboration of aldehydes originally reported by Antil…

C2-Symmetric Ferrocene-Bis(ureido)peptides : Synthesis, Conformation and Solid-State Structure

2009

The extension of peptide derivatives of ferrocene-1,1'-dicarboxylic acid by formal insertion of NH units between ferrocene and peptide strands results in ferrocene-bis(ureido)-peptides. Experimentally, alanine and dialanine methyl esters were attached to the 1- and 1'-position of 1,1'-diiso-cyanoferrocene to give the corresponding bis(ureido)peptide derivatives 3 and 4. The conformation of 3 has been determined in the solid state by X-ray crystallography. In solution the preferred conformation of 3 and 4 has been elucidated by NMR, IR and CD spectroscopy in concert with DFT calculations. The secondary structure of ferrocene―bis(ureido)peptides 3 and 4 is determined by double bifurcated intr…

Characterization of gas phase aggregates of bis(2-ethylhexyl)sulfosuccinate (AOT) and divalent metal ions. Elimination of radical species in the deco…

2012

Structure and properties of even-electron anionic species formed by bis(2-ethylhexyl)sulfosuccinate (AOT) and divalent metal ions (MII) with stoichiometry [AOTMIICl2]– have been investigated by using electrospray ionization and different mass spectrometry techniques, such as high resolution, accurate mass measurements, collision-induced dissociation (CID) multiple-stage mass spectrometry. Owing to CID, eliminations of neutrals, mainly consisting in hydrochloric acid, 2-ethyl-1-hexene and 2-ethylhexanol, and an unexpected loss of an alkyl radical have been observed. The radical anions [C4HO6SMIICl]–• so produced have been characterized by MS3 experiments. Density functional theory calculatio…

Structure and properties of N-methyl-N-(4-pyridyl)-nitramine and 1,4-dihydro-1-methyl-4-nitriminopyridine

2002

Abstract The molecular structure and spectral properties of N -methyl- N -(4-pyridyl)-nitramine ( 1 ) and 1,4-dihydro-1-methyl-4-nitriminopyridine ( 3 ) were investigated by the X-ray diffraction, FTIR, nuclear magnetic resonance (NMR) methods and DFT theoretical calculations. N -methyl- N -(4-pyridyl)-nitramine ( 1 ) crystallises in the orthorhombic Pbca space group. It is composed of two planar fragments; nitramino (N 2 O 2 ) group and the pirydyl ring. These two groups are twisted at about 70° with respect to each other, along the Ar–N bond. On the contrary, in compound 3 , they are coplanar to each other. Twist of the nitramino group in 1 with respect to the pirydyl ring leads to a sign…

DLPNO-CCSD(T) scaled methods for the accurate treatment of large supramolecular complexes

2017

In this work, we present scaled variants of the DLPNO-CCSD(T) method, dubbed as (LS)DLPNO-CCSD(T) and (NS)DLPNO-CCSD(T), to obtain accurate interaction energies in supramolecular complexes governed by noncovalent interactions. The novel scaled schemes are based on the linear combination of the DLPNO-CCSD(T) correlation energies calculated with the standard (LoosePNO and NormalPNO) and modified (Loose2PNO and Normal2PNO) DLPNO-CCSD(T) accuracy levels. The scaled DLPNO-CCSD(T) variants provide nearly TightPNO accuracy, which is essential for the quantification of weak noncovalent interactions, with a noticeable saving in computational cost. Importantly, the accuracy of the proposed schemes is…

Comparison of spin density calculation methods for various alkyl-substituted 9,10-anthraquinone anion radicals in the solution phase

1996

EPR and ENDOR spectra were recorded for 2-methyl-9,10-anthraquinone (2-methylAQ), 2-ethylAQ, 2-tertbutylAQ and 2,3-dimethylAQ anion radicals in the solution phase. The EPR spectra were simulated with the help of ENDOR data. The experimental isotropic hyperfine coupling constants (IHFCs) were compared with calculated values from semi-empirical INDO, spin-restricted AM1/CI and B3PW91 density-functional methods. The best computational methods for the IHFCs were the semi-empirical AM1/CI method and the B3PW91 density-functional method with a large basis set.

First Evidence of Proline Acting as a Bifunctional Catalyst in the Baylis–Hillman Reaction Between Alkyl Vinyl Ketones and Aryl Aldehydes

2008

Proline in the presence of sodium hydrogen carbonate has been found to be an effective catalyst for the Baylis–Hillman reaction between methyl or ethyl vinyl ketone and aryl aldehydes. Screening of several amine catalysts showed that an ionizable carboxylic function directly linked to the secondary amine catalyst plays an important role in the synthesis of the desired product in good yield. The data obtained has allowed us to suggest, for the first time, that proline, sarcosine, pipecolinic acid and homoproline may act as bifunctional catalysts via a bicyclic enaminolactone species as intermediate. Quantum-mechanical calculations (PM3/COSMO and ab initio 3-21G/COSMO) support this mechanism …