Complex dynamic behavior of fluctuating smectic- A films as studied by scattering with coherent X-rays

Coherent dynamic x-ray scattering has been used to study the thermally excited layer fluctuations in freely suspended smectic films of the compound 4O.8. Using 8-keV x rays and films with a thickness around 0.3 &mgr;m we resolve relaxation times down to a few &mgr;s. A combination of damped and oscillatory behavior is observed for the layer undulations, which can be attributed to inertial effects. These are due to the surface contribution to the free energy which cannot be disregarded for thin films.     

Chemistry of 4-alkylaryloxenium ion "precursors": sound and fury signifying something?

Quinol esters 2b, 2c, and 3b and sulfonamide 4c were investigated as possible precursors to 4-alkylaryloxenium ions, reactive intermediates that have not been previously detected. These compounds exhibit a variety of interesting reactions, but with one possible exception, they do not generate oxenium ions. The 4-isopropyl ester 2b predominantly undergoes ordinary acid- and base-catalyzed ester hydrolysis. The 4-tert-butyl ester 2c decomposes under both acidic and neutral conditions to generate tert-butanol and 1-acetyl-1,4-hydroquinone, 8, apparently by an SN1 mechanism. This is also a minor decomposition pathway for 2b, but the mechanism in that case is not likely to be SN1. Decomposition of 2c in the presence of N3- leads to formation of the explosive 2,3,5,6-tetraazido-1,4-benzoquinone, 14, produced by N3--induced hydrolysis of 8, followed by a series of oxidations and nucleophilic additions by N3-. No products suggestive of N3--trapping of an oxenium ion were detected. The 4-isopropyl dichloroacetic acid ester 3b reacts with N3- to generate the two adducts 2-azido-4-isopropylphenol, 5b, and 3-azido-4-isopropylphenol, 11b. Although 5b is the expected product of N3- trapping of the oxenium ion, kinetic analysis shows that it is produced by a kinetically bimolecular reaction of N3- with 3b. No oxenium ion is involved. The sulfonamide 4c predominantly undergoes a rearrangement reaction under acidic and neutral conditions, but a minor component of the reaction yields 4-tert-butylcresol, 17, and 2-azido-4-tert-butylphenol, 5c, in the presence of N3-. These products may indicate that 4c generates the oxenium ion 1c, but they are generated in very low yields (ca. 10%) so it is not possible to definitively conclude that 1c has been produced. If 1c has been generated, the N3--trapping data indicate that it is a very short-lived and reactive species in H2O. Comparisons with similarly reactive nitrenium ions indicate that the lifetime of 1c is ca. 20-200 ps if it is generated, so it must react by a preassociation process. Density functional theory calculations at the B3LYP/6-31G*//HF/6-31G* level coupled with kinetic correlations also indicate that the aqueous solution lifetimes of 1a-c are in the picosecond range.     

Dichlorocarbene Addition to

In contrast to the terminal phosphinidene complex PhPW(CO)(5) (2), which adds to [5]metacyclophane (1) in a 1,4-fashion, dichlorocarbene preferentially adds in a 1,2-fashion to the formal "anti-Bredt" type double bond of the aromatic ring of 1 to afford the norcaradiene 11b, which immediately rearranges to the bridged cycloheptatriene 12b and further by a [1,5] sigmatropic chlorine migration to the isomeric 13b as the first observable product. More slowly, the latter isomerizes via a dissociative mechanism to give 15b. A computational study supports the notion that the [1,5] chlorine migration in the rearrangement 12b --> 13b, for which an activation barrier of 70.2 kJ mol(-)(1) was calculated, is essentially concerted with minor charge separation. In contrast, the analogous [1,5] chlorine migration in the flat model compound 7,7-dichlorocycloheptatriene (12a) displays features of a dissociative pathway.     

The exchange of effective mesons between nucleons in nuclei

A study is made of the nuclear matter G-matrix. A method is developed which allows the determination of a local G-operator. This method is applied to analyse the correlations of the G-matrix, i.e. G without the bare interaction V, in terms of meson-exchange-type interactions. For a strong potential (REID) these effective mesons have masses which exceed 800 MeV implying very short-ranged correlations. For a weaker potential these correlations are somewhat longer ranged. The dominant feature of these G-operator correlations is found to be a strong scalar isoscalar attractive interaction which provides the binding of the nuclear system. By comparing with exact results for Landau parameters and binding energies it is shown that the approximation made with this local operator is excellent. A weak density dependence of the correlations is found and the structure of the Landau parameter ? is discussed. Finally it is proposed that this G-operator is a suitable object to study finite nuclei.     

The reaction mechanism of heavy ion scattering at intermediate energies

The contribution to the real and imaginary nucleus-nucleus (N-N) optical potential from nucleon-nucleon scattering in the medium is calculated in a local density approximation from a two Fermi sphere nuclear matter picture for the N-N collision. This reaction mechanism is shown to be dominant for ¹²C + ¹²C scattering at all considered energies (160 MeV < E_lab < 2250 MeV) giving a weakly energy dependent reaction cross section of about 900 mb. Inclusion of the collective 2⁺, 3^? excitations in a coupled channel calculations gives good agreement for both the measured elastic and inelastic 2⁺ cross section at E_lab = 1016 MeV. This fully microscopic parameter free calculation indicates that the energy dependence of the reaction cross section for this system is mostly due to the decrease of the collective contribution with increasing energy contrary to current theoretical models.