Pushing and pulling electrons: the effect on the heat of formation of trifluoromethyl compounds

The effect on heats of formation, of conjoined or proximate functional groups which can interact via polar or resonance effects, is examined using the –CF₃ group as a standard. Two metrics are applied: the difference in heat of formation of G–CF₃ and G–CH₃, where –G is a wide range of functional groups, and also the deviation of the heat of formation of G–CF₃ from the average of the heats of formation of G–G and CF₃–CF₃. This latter metric reveals both stabilizing and destabilizing effects on the heat of formation, of up to 60 kcal/mol, depending on the polar and resonance nature of the –G structure. The possibility of using such metrics as a correction the group additivity values is examined.     

Development of a practical solid-phase synthesis approach to 1,3,5-triazepan-2,6-diones

1,3,5-Triazepan-2,6-diones are a class of conformationally restricted heterocycles derived from dipeptides. With the aim to develop a general and practical method useful for library production, three polymer-assisted syntheses, all based on a catch and release approach, have been evaluated and compared. The method involving a Hofmann rearrangement of N-Boc dipeptide carboxamides and subsequent trapping of the isocyanate on polymer-supported N-hydroxysuccinimide (PS-HOSu) was found to be the most reliable and versatile, allowing rapid access to the 1,3,5-triazepan-2,6-dione skeleton.     

Incompressible quantum liquids and new conservation laws

In this Letter, we investigate a class of Hamiltonians which, in addition to the usual center-of-mass momentum conservation, also have center-of-mass position conservation. We find that, regardless of the particle statistics, the energy spectrum is at least q-fold degenerate when the filling factor is p/q, where and are coprime integers. Interestingly, the simplest Hamiltonian respecting this type of symmetry encapsulates two prominent examples of novel states of matter, namely, the fractional quantum Hall liquid and the quantum dimer liquid. We discuss the relevance of this class of Hamiltonian to the search for featureless Mott insulators.     

Dopant-modulated pair interaction in cuprate superconductors

A comparison of recent experimental STM data with single-impurity and many-impurity Bogoliubov-de Gennes calculations strongly suggests that random out-of-plane dopant atoms in cuprates modulate the pair interaction locally. This type of disorder is crucial to understanding the nanoscale electronic inhomogeneity observed in BSCCO-2212, and can reproduce observed correlations between the positions of impurity atoms and various aspects of the local density of states such as the gap magnitude and the height of the coherence peaks. Our results imply that each dopant atom modulates the pair interaction on a length scale of order one lattice constant.     

The Piracicaba River basin: isotope hydrology of a tropical river basin under anthropogenic stress

The stable isotope content of samples of precipitation and of the river water throughout the Piracicaba basin in Brazil was measured over a two-year period. The isotope values of precipitation follow a consistent pattern of relatively depleted values of both deuterium and oxygen 18 during the rainy summers and enriched ones during the dry winters, with all values aligned slightly above the Global Meteoric Water Line. The isotopic composition of the river water throughout the basin shows a remarkable spatial coherence and much smaller scatter of data than those of the precipitation. The isotope composition of river water is close to that of the precipitation in the rainy season, however, with a consistent lower d-excess value by 1/1000-2/1000. This is attributed to evaporative water loss in the basin, in part an expression of the recycling of water due to the anthropogenic activity in the region. The more divergent values are recorded during high-water stages in the rivers. In many cases, the floods during the beginning of the rainy season are characterized by an enrichment of the heavy isotopes and lower d-excess values when compared to the precipitation, with the opposite situation later in the rainy season. This is interpreted as resulting from the watershed/riverflow interaction pattern, and it thus suggests that the isotope composition can monitor the hydrologic situation in the basin and its changes.     

Chemisorption of 1,1-dichloroethene on the Si(1 1 1)-7 × 7 surface

Chemisorption of 1,1-dichloroethene (Cl₂CCH₂) to a Si(1 1 1)-7 × 7 surface was studied by means of X-ray photoelectron spectroscopy using synchrotron radiation, recording chlorine 2p and carbon 1s spectra. For carbon 1s, spectral assignment of the chemisorbed species is based on quantum chemical calculations of chemical shifts in model compounds.The results confirm the identity of covalently bonded 1-chlorovinyl (-CClCH₂) and vinylidene (CCH₂) adspecies. Upon chemisorption at room temperature it was found that about one-third of the molecules break one C-Cl bond while about two-thirds of the adsorbates break two C-Cl bonds. We do not, however, find evidence for isomerization of CCH₂ to di-bonded vinylene (-CHCH-).