3,552 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
Electric Field Enhanced Hydrogen Storage on BN Sheet
Using density functional theory we show that an applied electric field
substantially improves the hydrogen storage properties of a BN sheet by
polarizing the hydrogen molecules as well as the substrate. The adsorption
energy of a single H2 molecule in the presence of an electric field of 0.05
a.u. is 0.48 eV compared to 0.07 eV in its absence. When one layer of H2
molecules is adsorbed, the binding energy per H2 molecule increases from 0.03
eV in the field-free case to 0.14 eV/H2 in the presence of an electric field of
0.045 a.u. The corresponding gravimetric density of 7.5 wt % is consistent with
the 6 wt % system target set by DOE for 2010. Once the applied electric field
is removed, the stored H2 molecules can be easily released, thus making the
storage reversible.Comment: submitted to Phys. Rev. Lett. 15 pages with 6 figure
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
Quasiparticle bandgap engineering of graphene and graphone on hexagonal boron nitride substrate
Graphene holds great promise for post-silicon electronics, however, it faces
two main challenges: opening up a bandgap and finding a suitable substrate
material. In principle, graphene on hexagonal boron nitride (hBN) substrate
provides potential system to overcome these challenges. Recent theoretical and
experimental studies have provided conflicting results: while theoretical
studies suggested a possibility of a finite bandgap of graphene on hBN, recent
experimental studies find no bandgap. Using the first-principles density
functional method and the many-body perturbation theory, we have studied
graphene on hBN substrate. A Bernal stacked graphene on hBN has a bandgap on
the order of 0.1 eV, which disappears when graphene is misaligned with respect
to hBN. The latter is the likely scenario in realistic devices. In contrast, if
graphene supported on hBN is hydrogenated, the resulting system (graphone)
exhibits bandgaps larger than 2.5 eV. While the bandgap opening in graphene/hBN
is due to symmetry breaking and is vulnerable to slight perturbation such as
misalignment, the graphone bandgap is due to chemical functionalization and is
robust in the presence of misalignment. The bandgap of graphone reduces by
about 1 eV when it is supported on hBN due to the polarization effects at the
graphone/hBN interface. The band offsets at graphone/hBN interface indicate
that hBN can be used not only as a substrate but also as a dielectric in the
field effect devices employing graphone as a channel material. Our study could
open up new way of bandgap engineering in graphene based nanostructures.Comment: 8 pages, 4 figures; Nano Letters, Publication Date (Web): Oct. 25
2011, http://pubs.acs.org/doi/abs/10.1021/nl202725
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
First Order Static Excitation Potential: Scheme for Excitation Energies and Transition Moments
We present an approximation scheme for the calculation of the principal
excitation energies and transition moments of finite many-body systems. The
scheme is derived from a first order approximation to the self energy of a
recently proposed extended particle-hole Green's function. A hermitian
eigenvalue problem is encountered of the same size as the well-known Random
Phase Approximation (RPA). We find that it yields a size consistent description
of the excitation properties and removes an inconsistent treatment of the
ground state correlation by the RPA. By presenting a hermitian eigenvalue
problem the new scheme avoids the instabilities of the RPA and should be well
suited for large scale numerical calculations. These and additional properties
of the new approximation scheme are illuminated by a very simple exactly
solvable model.Comment: 15 pages revtex, 1 eps figure included, corrections in Eq. (A1) and
Sec. II
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
Overturning established chemoselectivities : selective reduction of arenes over malonates and cyanoacetates by photoactivated organic electron donors
The prevalence of metal-based reducing reagents, including metals, metal complexes, and metal salts, has produced an empirical order of reactivity that governs our approach to chemical synthesis. However, this reactivity may be influenced by stabilization of transition states, intermediates, and products through substrate-metal bonding. This article reports that in the absence of such stabilizing interactions, established chemoselectivities can be overthrown. Thus, photoactivation of the recently developed neutral organic superelectron donor 5 selectively reduces alkyl-substituted benzene rings in the presence of activated esters and nitriles, in direct contrast to metal-based reductions, opening a new perspective on reactivity. The altered outcomes arising from the organic electron donors are attributed to selective interactions between the neutral organic donors and the arene rings of the substrates
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