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[structure: see text] Two sequential transition states are calculated at the B3LYP/6-31G(d,p) level for the deazetization of 3b. The intrinsic reaction coordinate for loss of nitrogen passes through a transition state and then a valley-ridge inflection point and ultimately leads to the transition state for the Cope rearrangement of semibullvalene 4b. The energetic and geometrical consequences are discussed. 相似文献
34.
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36.
Summary This paper contains three applications of the technique of limit series (our [1986]) to the theory of ramification of linear series on smooth curves, and curves of compact type, overC.Let {L
t
t|<}, be a family of linear series on a smooth family of smooth curves {C
t
}, and letp
1(t),p
2(t)C
t
be sections of the family which coincide (only) att=0. Setp=p
1())=p
2(0)C
0.We first give a condition related to the Schubert calculus which must be satisfied by the ramification series
and the
. We then take up the converse problem: In what ways can a given ramification point arise as a limit? We show that if the ramification point isdimensionally proper in the sense of our [1986], then families of every kind allowed by the Schubert calculus condition can actually be constructed. Finally, we prove that dimensional propriety is in a strong sense an open condition, so that ramification points constructed as above are again dimensionally proper.In the body of the paper we work not with pairs of points, as above, but with arbitrary finite collections of points approaching (possibly) several points of the limit curve. Further, by their nature, the results are valid for families of curves of compact type. 相似文献
37.
The equality of two critical points — the percolation thresholdp
H
and the pointp
T
where the cluster size distribution ceases to decay exponentially — is proven for all translation invariant independent percolation models on homogeneousd-dimensional lattices (d1). The analysis is based on a pair of new nonlinear partial differential inequalities for an order parameterM(,h), which forh=0 reduces to the percolation densityP
— at the bond densityp=1–e
–
in the single parameter case. These are: (1)MhM/h+M
2+MM/, and (2) M/|J|MM/h. Inequality (1) is intriguing in that its derivation provides yet another hint of a 3 structure in percolation models. Moreover, through the elimination of one of its derivatives, (1) yields a pair of ordinary differential inequalities which provide information on the critical exponents
and . One of these resembles an Ising model inequality of Fröhlich and Sokal and yields the mean field bound 2, and the other implies the result of Chayes and Chayes that
. An inequality identical to (2) is known for Ising models, where it provides the basis for Newman's universal relation
and for certain extrapolation principles, which are now made applicable also to independent percolation. These results apply to both finite and long range models, with or without orientation, and extend to periodic and weakly inhomogeneous systems.Research supported in part by the NSF Grant PHY-8605164Also in the Physics Department 相似文献
38.
David Akers 《International Journal of Theoretical Physics》1987,26(12):1169-1173
Recently evidence was presented for the existence of magnetic charge from Zeeman splitting in meson states. The model by Akers predicted the existence of a new meson at 1814 MeV withI
G(J
PC
)=0+(0–+). Experimental evidence for this new meson is cited and discussed. 相似文献
39.
Summary Electron microscope examination of thixotropic aluminium and thorium molybdate gels shows that one hour after formation they are constituted by short fibrils of small axial ratio. The fibrils of the aluminium molybdate gels, with ageing at room temperature or with boiling, increase in diameter and length; the fibrous shape of the particles is maintained after two and a half years of ageing; all fibrils are crystalline by electron diffraction. The fibrils of the thorium molybdate gels, except in the gels containing hydrochloric acid, change with ageing at room temperature or with boiling, into plates of hexagonal, elliptical or rectangular profile; the fibrils and plates are crystalline and have the same electron diffraction pattern as the fibrils.This work was aided, in part, by grants from Conselho Nacional de Pesquisas and the Rockefeller Foundation. 相似文献
40.
David W. Schwenke 《Theoretical chemistry accounts》1988,74(5):381-402
A new method for the direct calculation of resonance parameters is presented. It is based upon searching for poles of the scattering matrix at complex energies. This search is expedited by the use of analytic derivatives of the scattering matrix with respect to the total energy. This procedure is applied initially to a single channel problem, but is generalizable to more complicated systems. Using the most accurate available potential energy data, we calculate resonance parameters for all of the physically important quasibound states of the ground electronic state of the hydrogen molecule. Corrections to the Born-Oppenheimer potential are included and assessed. The new method has no difficulty locating resonances with widths greater than about 1×10–7 cm–1. It is easier to find narrow resonances by monitoring the dependence of the imaginary part of the reactance matrix on the real part of a complex energy than to monitor the dependence of the eigenphase sum on energy at real energies. 相似文献