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Matter - a current picture. - Science progress
A century ago, a two-part review by W. C. McC. Lewis entitled "The Structure of Matter" appeared in this journal, surveying the achievements that had been made to date in that field. Topics included the value of Avogadro's constant, the dimensions of a molecule, equations of state for non-ideal gases, then-current theories relating electron configurations to the Periodic Law, the then-new nuclear atom model of Rutherford, and the first findings from X-ray crystallographic studies of matter, a field then in its nascent phase. This article is a sequel to that work. As a vast quantity of research has been addressed to the topic in the intervening period, the view presented here can at best be selective and idiosyncratic. Nonetheless, it attempts to capture some of the important strides in 'matter science', broadly defined, over the past century, highlight some recent areas of interest or novelty, and give a picture of some of the mysteries that remain.
Puzzles in bonding and spectroscopy: the case of dicarbon. - Science progress
The unstable molecule Câ‚‚ has been of interest since its identification as the source of the "Swan band" features observable in the spectra offlames, carbon arcs, white dwarf stars, and comets, and it continues to serve as a focal point for experimental and theoretical discovery. Recent spectroscopic work has identified a quintet state of the molecule for the first time, while new insights into the bond order of Câ‚‚ in its ground state have been provided by sophisticated computational methods based on valence bond theory. This article gives a review of spectroscopic and computational work on Câ‚‚ including both historical background and the most recent discoveries.
"Vibrational bonding": a new type of chemical bond is discovered. - Science progress
A long-sought but elusive new type of chemical bond, occurring on a minimum-free, purely repulsive potential energy surface, has recently been convincingly shown to be possible on the basis of high-level quantum-chemical calculations. This type of bond, termed a vibrational bond, forms because the total energy, including the dynamical energy of the nuclei, is lower than the total energy of the dissociated products, including their vibrational zero-point energy. For this to be the case, the ZPE of the product molecule must be very high, which is ensured by replacing a conventional hydrogen atom with its light isotope muonium (Mu, mass = 1/9 u) in the system Br-H-Br, a natural transition state in the reaction between Br and HBr. A paramagnetic species observed in the reaction Mu +Br2 has been proposed as a first experimental sighting of this species, but definitive identification remains challenging.
Isotopes and analogs of hydrogen--from fundamental investigations to practical applications. - Science progress
Hydrogen has a central role in the story of the universe itself and also in the story of our efforts to understand it. This paper retells the story of the part played by hydrogen and its stable isotope deuterium in the primordial synthesis of the elements, then goes on to describe how the spectrum of atomic hydrogen led to insights into the laws governing matter at the most fundamental level, from the quantum mechanics of SchrÃ¶dinger and Heisenberg, through quantum electrodynamics, to the most recent work investigating the underlying structure of the proton itself. Atomic hydrogen is unique among the elements in that the concept of isotopy--atoms having the same nuclear charge but different masses--is stretched to its limit in the isotopes of hydrogen, ranging from the well-known isotopes deuterium and tritium to exotic species such as muonium, muonic helium, and positronium. These atoms, or atom-like objects, have much to tell us about fundamental aspects of the universe. In recent years the idea of utilizing hydrogen either as an energy source (through nuclear fusion) or as an energy storage medium (bound in hydrides or other materials) has attracted much attention as a possible avenue to a post-oil energy future. Some of the more interesting recent developments are described here. Dedicated to the memory of Brian C. Webster (1939-2008).
New results for the formation of a muoniated radical in the Mu + Br2 system: a van der Waals complex or evidence for vibrational bonding in Br-Mu-Br? - Physical chemistry chemical physics : PCCP
New evidence is presented for the observation of a muoniated radical in the Mu + Br(2) system, from Î¼SR longitudinal field (LF) repolarisation studies in the gas phase, at Br(2) concentrations of 0.1 bar in a Br(2)/N(2) mixture at 300 K and at 10 bar total pressure. The LF repolarisation curve, up to a field of 4.5 kG, reveals two paramagnetic components, one for the Mu atom, formed promptly during the slowing-down process of the positive muon, with a known Mu hyperfine coupling constant (hfcc) of 4463 MHz, and one for a muoniated radical formed by fast Mu addition. From model fits to the Br(2)/N(2) data, the radical component is found to have an unusually high muon hfcc, assessed to be âˆ¼3300 MHz with an overall error due to systematics expected to exceed 10%. This high muon hfcc is taken as evidence for the observation of either the Br-Mu-Br radical, and hence of vibrational bonding in this H[combining low line]-L[combining low line]-H[combining low line] system, or of a MuBr(2) van der Waals complex formed in the entrance channel. Preliminary ab initio electronic structure calculations suggest the latter is more likely but fully rigorous calculations of the effect of dynamics on the hfcc for either system have yet to be carried out.
Providing dental care to patients with developmental disabilities. An introduction for the private practitioner. - The New York state dental journal
During the past 20 to 25 years, in New York State, most individuals with developmental disabilities who had previously been housed in large institutions have been mainstreamed into community-based residences. This shift has created a need for dental services in the community. The article presented here provides information and tips to assist the general practitioner with integrating these patients into a private practice setting.
Hydrogen and deuterium atoms in octasilsesquioxanes: experimental and computational studies. - Journal of the American Chemical Society
The rate of detrapping of atomic hydrogen from several octasilsesquioxanes is the same for dissolved and solid samples and is independent of the presence of other species such as free radicals or oxygen; varying the cage substituents leads to only minor differences in the activation parameters. Hydrogen atoms are found to be more strongly stabilized in homosubstituted octasilsesquioxanes compared with singly Ge-substituted cages. A kinetic isotope effect observed for the detrapping of H and D from MeT(8) is ascribed to the difference in the zero-point energies of the trapped atoms. There is a secondary H/D isotope effect in the temperature dependence of the (29)Si-superhyperfine splitting constants in the range 228-353 K. Cage relaxation has a substantial effect on the detrapping barrier but little influence on the intracage potential. Calculations using a rigid cage approximation give satisfactory agreement with zero-point parameters extracted from experimental data. Different model chemistries yield qualitatively different pictures of the dependence of the hyperfine coupling constant of the trapped H atom upon the detrapping coordinate. Within an isotropic approximation of the vibrational displacements, the B3LYP data give fairly close agreement with the experimental temperature dependence, subject to a shift of the absolute value related to known weaknesses of the method. For the Si(7)Ge cage, it is found that the transition state in which the H atom passes through a Ge-containing face is strongly favored, accounting for the larger detrapping rate parameters observed experimentally for this species.
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83 Haviland Dr Patterson, NY 12563
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