170,394 research outputs found
Assessment of W1 and W2 theories for the computation of electron affinities, ionization potentials, heats of formation, and proton affinities
The performance of two recent {\em ab initio} computational thermochemistry
schemes, W1 and W2 theory [J.M.L. Martin and G. de Oliveira, J. Chem. Phys.
111, 1843 (1999}], is assessed for an enlarged sample of thermochemical data
consisting of the ionization potentials and electron affinities in the G2-1 and
G2-2 sets, as well as the heats of formation in the G2-1 and a subset of the
G2-2 set. We find W1 theory to be several times more accurate for ionization
potentials and electron affinities than commonly used (and less expensive)
computational thermochemistry schemes such as G2, G3, and CBS-QB3: W2 theory
represents a slight improvement for electron affinities but no significant one
for ionization potentials. The use of a two-point rather than a
three-point extrapolation for the SCF component greatly enhances the
numerical stability of the W1 method for systems with slow basis set
convergence. Inclusion of first-order spin-orbit coupling is essential for
accurate ionization potentials and electron affinities involving degenerate
electronic states: inner-shell correlation is somewhat more important for
ionization potentials than for electron affinities, while scalar relativistic
effects are required for the highest accuracy. The mean deviation from
experiment for the G2-1 heats of formation is within the average experimental
uncertainty. W1 theory appears to be a valuable tool for obtaining benchmark
quality proton affinities.Comment: Journal of Chemical Physics, in press (303115JCP). 2 RevTeX files,
first is text and tables, second is E-PAPS tables S-1 through S-5. Additional
supplementary material (total energies, basis function exponents) available
at http://theochem.weizmann.ac.il/web/papers/w1w2.htm
A bilayer Double Semion Model with Symmetry-Enriched Topological Order
We construct a new model of two-dimensional quantum spin systems that
combines intrinsic topo- logical orders and a global symmetry called flavour
symmetry. It is referred as the bilayer Doubled Semion model (bDS) and is an
instance of symmetry-enriched topological order. A honeycomb bi- layer lattice
is introduced to combine a Double Semion Topolgical Order with a global
spin-flavour symmetry to get the fractionalization of its quasiparticles. The
bDS model exhibits non-trival braid- ing self-statistics of excitations and its
dual model constitutes a Symmetry-Protected Topological Order with novel edge
states. This dual model gives rise to a bilayer Non-Trivial Paramagnet that is
invariant under the flavour symmetry and the well-known spin flip symmetry.Comment: revtex4 file, color figure
Fully ab initio atomization energy of benzene via W2 theory
The total atomization energy at absolute zero, (TAE) of benzene,
CH, was computed fully {\em ab initio} by means of W2h theory as 1306.6
kcal/mol, to be compared with the experimentally derived value 1305.7+/-0.7
kcal/mol. The computed result includes contributions from inner-shell
correlation (7.1 kcal/mol), scalar relativistic effects (-1.0 kcal/mol), atomic
spin-orbit splitting (-0.5 kcal/mol), and the anharmonic zero-point vibrational
energy (62.1 kcal/mol). The largest-scale calculations involved are
CCSD/cc-pV5Z and CCSD(T)/cc-pVQZ; basis set extrapolations account for 6.3
kcal/mol of the final result. Performance of more approximate methods has been
analyzed. Our results suggest that, even for systems the size of benzene,
chemically accurate molecular atomization energies can be obtained from fully
first-principles calculations, without resorting to corrections or parameters
derived from experiment.Comment: J. Chem. Phys., accepted. RevTeX, 12 page
Some Observations on the Performance of the Most Recent Exchange-Correlation Functionals for the Large and Chemically Diverse GMTKN55 Benchmark
Benchmarks that span a broad swath of chemical space, such as GMTKN55, are
very useful for assessing progress in the quest for more universal DFT
functionals. We find that the WTMAD2 metrics for a great number of functionals
show a clear "Jacob's Ladder hierarchy"; that the "combinatorial" development
strategy of Head-Gordon and coworkers generates "best on rung" performers; that
the quality of the nonlocal dispersion correction becomes more important as
functionals become more accurate for nondispersion properties; that fitting
against small, unrepresentative benchmark sets leads to underperforming
functionals; and that {\omega}B97M(2) is currently the best DFT functional of
any kind, but that revDSD-D4 functionals are able to reach similar performance
using fewer parameters, and that revDOD-D4 in addition permits reduced-scaling
algorithms. If one seeks a range-separated hybrid (RSH) GGA that also performs
well for optical excitation energies, CAM-QTP-01 may be a viable option. The D4
dispersion model, with its partial charge dependence, appears to be clearly
superior to D3BJ and even possibly NL. Should one require a double hybrid
without dispersion model, noDispSD-SCAN is a viable option. Performance for the
MOBH35 transition metal benchmark is different: the best double hybrids are
competitive but not superior to {\omega}B97M-V, which offers the best
performance compromise for mixed main group-transition metal problems.Comment: 5 pages (ICCMSE-2019 conference proceedings), AIP Conference
Proceedings, in pres
A definitive heat of vaporization of silicon through benchmark ab initio calculations on SiF_4
In order to resolve a significant uncertainty in the heat of vaporization of
silicon -- a fundamental parameter in gas-phase thermochemistry -- [Si(g)] has been determined from a thermochemical cycle involving
the precisely known experimental heats of formation of SiF_4(g) and F(g) and a
benchmark calculation of the total atomization energy (TAE_0) of SiF_4 using
coupled-cluster methods. Basis sets up to on Si and
on F have been employed, and extrapolations for residual basis
set incompleteness applied. The contributions of inner-shell correlation (-0.08
kcal/mol), scalar relativistic effects (-1.88 kcal/mol), atomic spin-orbit
splitting (-1.97 kcal/mol), and anharmonicity in the zero-point energy (+0.04
kcal/mol) have all been explicitly accounted for. Our benchmark TAE_0=565.89
\pm 0.22 kcal/mol leads to [Si(g)]=107.15 \pm 0.38
kcal/mol ([Si(g)]=108.19 \pm 0.38 kcal/mol): between
the JANAF/CODATA value of 106.5 \pm 1.9 kcal/mol and the revised value proposed
by Grev and Schaefer [J. Chem. Phys. 97, 8389 (1992}], 108.1 \pm 0.5 kcal/mol.
The revision will be relevant for future computational studies on heats of
formation of silicon compounds.Comment: J. Phys. Chem. A, submitted Feb 1, 199
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