3,295 research outputs found
Performance of ab initio and density functional methods for conformational equilibria of CnH2n+2 alkane isomers (n=2-8)
Conformational energies of n-butane, n-pentane, and n-hexane have been
calculated at the CCSD(T) level and at or near the basis set limit.
Post-CCSD(T) contribution were considered and found to be unimportant. The data
thus obtained were used to assess the performance of a variety of density
functional methods. Double-hybrid functionals like B2GP-PLYP and B2K-PLYP,
especially with a small Grimme-type empirical dispersion correction, are
capable of rendering conformational energies of CCSD(T) quality. These were
then used as a `secondary standard' for a larger sample of alkanes, including
isopentane and the branched hexanes as well as key isomers of heptane and
octane. Popular DFT functionals like B3LYP, B3PW91, BLYP, PBE, and PBE0 tend to
overestimate conformer energies without dispersion correction, while the M06
family severely underestimates GG interaction energies. Grimme-type dispersion
corrections for these overcorrect and lead to qualitatively wrong conformer
orderings. All of these functionals also exhibit deficiencies in the conformer
geometries, particularly the backbone torsion angles. The PW6B95 and, to a
lesser extent, BMK functionals are relatively free of these deficiencies.
Performance of these methods is further investigated to derive conformer
ensemble corrections to the enthalpy function, , and the Gibbs
energy function, , of these alkanes. While
is only moderately sensitive to the level of theory, exhibits more pronounced sensitivity. Once again, double hybrids
acquit themselves very well.Comment: J. Phys. Chem. A, revised [Walter Thiel festschrift
Accurate Treatment of Large Supramolecular Complexes by Double-Hybrid Density Functionals Coupled with Nonlocal van der Waals Corrections
In this work, we present a thorough assessment of the performance of some representative double-hybrid density functionals (revPBE0-DH-NL and B2PLYP-NL) as well as their parent hybrid and GGA counterparts, in combination with the most modern version of the nonlocal (NL) van der Waals correction to describe very large weakly interacting molecular systems dominated by noncovalent interactions. Prior to the assessment, an accurate and homogeneous set of reference interaction energies was computed for the supramolecular complexes constituting the L7 and S12L data sets by using the novel, precise, and efficient DLPNO-CCSD(T) method at the complete basis set limit (CBS). The correction of the basis set superposition error and the inclusion of the deformation energies (for the S12L set) have been crucial for obtaining precise DLPNO-CCSD(T)/CBS interaction energies. Among the density functionals evaluated, the double-hybrid revPBE0-DH-NL and B2PLYP-NL with the three-body dispersion correction provide remarkably accurate association energies very close to the chemical accuracy. Overall, the NL van der Waals approach combined with proper density functionals can be seen as an accurate and affordable computational tool for the modeling of large weakly bonded supramolecular systems.Financial support by the “Ministerio de Economía y Competitividad” (MINECO) of Spain and European FEDER funds through projects CTQ2011-27253 and CTQ2012-31914 is acknowledged. The support of the Generalitat Valenciana (Prometeo/2012/053) is also acknowledged. J.A. thanks the EU for the FP7-PEOPLE-2012-IEF-329513 grant. J.C. acknowledges the “Ministerio de Educación, Cultura y Deporte” (MECD) of Spain for a predoctoral FPU grant
State-dependent or time-dependent pricing? New evidence from a monthly firm-level survey: 1980-2017
We examine the relative importance of time and state dependence in the price-setting decisions of firms using a monthly panel of German firms over the period 1980–2017. We propose a refined version of time dependence by introducing different hazard functions for price increases and decreases. We find three sets of results. First, time dependence is much more important for price setting than what the previous literature has found. Second, price decreases can be well explained by time dependence alone. Price increases are best predicted by the interaction of time-dependent and firm-specific state factors. Third, time dependence for price increases and decreases look completely different from each other. Our empirical results support the notion that theoretical models should integrate both time and state dependence
Elastic and vibrational properties of alpha and beta-PbO
The structure, electronic and dynamic properties of the two layered alpha
(litharge) and beta (massicot) phases of PbO have been studied by density
functional methods. The role of London dispersion interactions as leading
component of the total interaction energy between layers has been addressed by
using the Grimme's approach, in which new parameters for Pb and O atoms have
been developed. Both gradient corrected and hybrid functionals have been
adopted using Gaussian-type basis sets of polarized triple zeta quality for O
atoms and small core pseudo-potential for the Pb atoms. Basis set superposition
error (BSSE) has been accounted for by the Boys-Bernardi correction to compute
the interlayer separation. Cross check with calculations adopting plane waves
that are BSSE free have also been performed for both structures and vibrational
frequencies. With the new set of proposed Grimme's type parameters structures
and dynamical parameters for both PbO phases are in good agreement with
experimental data.Comment: 8 pages, 5 figure
Modeling interstellar amorphous solid water grains by tight-binding based methods: comparison between GFN-XTB and CCSD(T) results for water clusters
One believed path to Interstellar Complexes Organic Molecules (iCOMs)
formation inside the Interstellar Medium (ISM) is through chemical
recombination at the surface of amorphous solid water (ASW) mantle covering the
silicate-based core of the interstellar grains. The study of these iCOMs
formation and their binding energy to the ASW, using computational chemistry,
depends strongly on the ASW models used, as different models may exhibit sites
with different adsorbing features. ASW extended models are rare in the
literature because large sizes require very large computational resources when
quantum mechanical methods based on DFT are used. To circumvent this problem,
we propose to use the newly developed GFN-xTB Semi-empirical Quantum Mechanical
(SQM) methods from the Grimme's group. These methods are, at least, two orders
of magnitude faster than conventional DFT, only require modest central memory,
and in this paper we aim to benchmark their accuracy against rigorous and
resource hungry quantum mechanical methods. We focused on 38 water structures
studied by MP2 and CCSD(T) approaches comparing energetic and structures with
three levels of GFN-xTB parametrization (GFN0, GFN1, GFN2) methods. The
extremely good results obtained at the very cheap GFN-xTB level for both water
cluster structures and energetic paved the way towards the modeling of very
large AWS models of astrochemical interest.Comment: 9 pages, 4 figures, Submitted to LNCS (Springer) ICCSA202
What is the Role of Acid-Acid Interactions in Asymmetric Phosphoric Acid Organocatalysis? A Detailed Mechanistic Study using Interlocked and Non-Interlocked Catalysts
Organocatalysis has revolutionized asymmetric synthesis. However, the supramolecular interactions of organocatalysts in solution are often neglected, although the formation of catalyst aggregates can have a strong impact on the catalytic reaction. For phosphoric acid based organocatalysts, we have now established that catalyst-catalyst interactions can be suppressed by using macrocyclic catalysts, which react predominantly in a monomeric fashion, while they can be favored by integration into a bifunctional catenane, which react mainly as phosphoric acid dimers. For acyclic phosphoric acids, we found a strongly concentration dependent behavior, involving both monomeric and dimeric catalytic pathways. Based on a detailed experimental analysis, DFT-calculations and a direct NMR-based observation of the catalyst aggregates, we could demonstrate that intermolecular acid-acid interactions have a drastic influence on the reaction rate and stereoselectivity of the asymmetric transfer-hydrogenation catalyzed by chiral phosphoric acids
Spin states of zigzag-edged Mobius graphene nanoribbons from first principles
Mobius graphene nanoribbons have only one edge topologically. How the
magnetic structures, previously associated with the two edges of zigzag-edged
flat nanoribbons or cyclic nanorings, would change for their Mobius
counterparts is an intriguing question. Using spin-polarized density functional
theory, we shed light on this question. We examine spin states of zigzag-edged
Mobius graphene nanoribbons (ZMGNRs) with different widths and lengths. We find
a triplet ground state for a Mobius cyclacene, while the corresponding
two-edged cyclacene has an open-shell singlet ground state. For wider ZMGNRs,
the total magnetization of the ground state is found to increase with the
ribbon length. For example, a quintet ground state is found for a ZMGNR. Local
magnetic moments on the edge carbon atoms form domains of majority and minor
spins along the edge. Spins at the domain boundaries are found to be
frustrated. Our findings show that the Mobius topology (i.e., only one edge)
causes ZMGNRs to favor one spin over the other, leading to a ground state with
non-zero total magnetization.Comment: 17 pages, 4 figure
Contribution to the understanding of tribological properties of graphite intercalation compounds with metal chloride
Intrinsic tribological properties of lamellar compounds are usually attributed to the presence of van der Waals gaps in their structure through which interlayer interactions are weak. The controlled variation of the distances and interactions between graphene layers by intercalation of electrophilic species in graphite is used in order to explore more deeply the friction reduction properties of low-dimensional compounds. Three graphite intercalation compounds with antimony pentachloride, iron trichloride and aluminium trichloride are studied. Their tribological properties are correlated to their structural parameters, and the interlayer interactions are deduced from ab initio bands structure calculations
Asymmetric triplex metallohelices with high and selective activity against cancer cells
Small cationic amphiphilic α-helical peptides are emerging as agents for the treatment of cancer and infection, but they are costly and display unfavourable pharmacokinetics. Helical coordination complexes may offer a three-dimensional scaffold for the synthesis of mimetic architectures. However, the high symmetry and modest functionality of current systems offer little scope to tailor the structure to interact with specific biomolecular targets, or to create libraries for phenotypic screens. Here, we report the highly stereoselective asymmetric self-assembly of very stable, functionalized metallohelices. Their anti-parallel head-to-head-to-tail ‘triplex’ strand arrangement creates an amphipathic functional topology akin to that of the active sub-units of, for example, host-defence peptides and p53. The metallohelices display high, structure-dependent toxicity to the human colon carcinoma cell-line HCT116 p53++, causing dramatic changes in the cell cycle without DNA damage. They have lower toxicity to human breast adenocarcinoma cells (MDA-MB-468) and, most remarkably, they show no significant toxicity to the bacteria methicillin-resistant Staphylococcus aureus and Escherichia coli.
At a glanc
Excited States of Ladder-type Poly-p-phenylene Oligomers
Ground state properties and excited states of ladder-type paraphenylene
oligomers are calculated applying semiempirical methods for up to eleven
phenylene rings. The results are in qualitative agreement with experimental
data. A new scheme to interpret the excited states is developed which reveals
the excitonic nature of the excited states. The electron-hole pair of the
S1-state has a mean distance of approximately 4 Angstroem.Comment: 24 pages, 21 figure
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