The energetics of naphthalene derivatives,III: phenylacetic acid and the isomeric 1- and 2-naphthylacetic acids

Phenylacetic acid and the isomeric 1- and 2-naphthylacetic acids are at the confluence of diverse concepts, techniques and classes of organic compounds. Summing the results of our new enthalpy of formation of the gaseous phenylacetic acid reported herein, and of literature enthalpy of formation of the isomeric solid naphthylacetic acids and of our new sublimation enthalpies reported herein, we derive gas phase enthalpies of formation of ?314.7±3.1, ?246.9±2.0 and ?247.4±2.1kJmol^?1 respectively. This corresponds to 1- and 2-naphthylacetic acid having indistinguishable enthalpies of formation. We also performed MP2(full)/6-31G(d) calculations on these species, resulting in enthalpies of formation of ?307.3±0.8, ?247.4±3.4 and ?247.5±3.4kJmol^?1 for phenylacetic acid and 1- and 2-naphthylacetic acid in satisfactory agreement with the above experimental results.     

The mechanics and energetics of macromolecular interfaces

The fundamental concepts indicative of macromolecular interfaces are developed in a self consistent manner. The interfacial literature dealing with pure polymers and polymer solutions is reviewed in detail. Some of the difficulties associated with the definition and measurement of surface tension of macromolecular systems are discussed. An attempt is made to assess the level of development of the entire subject.     

The structure and energetics of carbon-nitrogen clusters

The structures and energies of clusters of carbon and nitrogen with up to 12 atoms have been investigated by density functional theory using the hybrid B3LYP functional and the cc-pVTZ basis set. This is the first systematic study of these clusters. Geometries are reported for the lowest energy states at this level of theory. Linear structures tend to be the global minima for clusters containing one or two nitrogen atoms, and patterns in the electronic structure of these clusters are reported. More complex branched structures lie close in energy to the linear conformations and, for clusters greater than six atoms and containing three or more nitrogen atoms, these branched structures are the minimum energy conformers. Comparisons are made with pure carbon and silicon-carbon clusters.     

Economics of isomeric energy

A high energy density source based on nuclear isomers may be conceptually attractive; but it is unrealistic if the energy’s price is too excessive. This paper estimates the price of isomeric energy, and shows that isomers can become practical only for low-energy applications.     

On the energetics of the Gamow-Teller resonances

It is suggested that the energy difference between the Gamow-Teller and Fermi resonances is given in units of MeV, by ${}^{\mathrm{E}}\text{GT}\text{?}{}^{\mathrm{E}}\text{F}\text{=26A}{}^{\mathrm{<mtext>?</mtext><mtext>1</mtext><mtext>3</mtext>}}\text{?18.5 (N ? Z)/A}$. The consequences of this result on the strength of the spin and isospin-dependent residual interaction, as well as on the effective axial-vector coupling constant, are discussed.     

Location of the181Os isomeric state

The decay of¹⁸¹Ir has been studied on-line with mass-separated sources from the ISOCELE facility. The level scheme of¹⁸¹ Os has been established. The isomeric state has been located at 48.9 keV above the ground state. Thus the isomeric and ground states are identified as the 7/2?(T1/2 =2.7 m) and 1/2?(T1/2=105 m) levels respectively.     

The structure and energetics of defects in liquid crystals

The study of defects in ordered media has become a subject of considerable interest to condensed matter physicists in recent years. This article presents a systematic account of the structures, energies and interactions of defects in the nematic, smectic, cholesteric and discotic phases of liquid crystals. Relevant experimental observations are also described.     

The g-factors of isomeric states in127, 128Xe

Excited states in^{127, 128}Xe were populated in the reaction⁹Be+¹²²Sn atE _lab=38 MeV. The de-excitation of the isomeric states 7/2⁺ in¹²⁷Xe and 8^? in¹²⁸Xe was studied using angular distribution and TDPAD methods on molten¹²²Sn targets. The results are $$\begin{gathered} T_{1/2} (7/2^ + ) = 37 \pm 1 ns, g(7/2^ + ) = + 0.241 \pm 0.009 \hfill \\ T_{1/2} (8^ - ) = 83 \pm 2 ns, g(8^ - ) = - 0.036 \pm 0.009. \hfill \\ \end{gathered}$$ The experimentalg-factors suggest the main configurationsvg _7/2 andvh _11/2 g _7/2 for the isomeric states. Detailed analysis of the combined information fromg-factors and transition rates set stringent limits on the admixtures of the wave functions. The quasirotational bands built on the two-quasiparticle 6^? and 10⁺ states are extended to higher spins, (14^?) and (16⁺), respectively, and their structures are analyzed within the framework of the Interacting Boson Model.     

Calculation of the ratio of isomeric cross sections

A new, more rigorous method for calculating the ratio of isomeric cross sections has been developed. The method is particularly valuable when the energy and spin distribution are known before the gamma rays populating the isomeric and ground states start to cascade. The usefulness of the method was demonstrated by applying it to the analysis of the ratio of isomeric cross sections in the ¹⁹⁶Hg(n,γ)¹⁹⁷Hg reaction, which was initiated by thermal neutrons.     

The energetics of large Lennard-Jones clusters: transition to the hexagonal close-packed structure

The energetics of large multiply twined particles (MTPs) such as decahedra with fivefold symmetry, face-centred cubic (fcc) and hexagonal close-packed (hcp) clusters in size from 2000 to ~45000 atoms was numerically analysed. Clusters were relaxed freely under the Lennard-Jones pair potential to the energy minimum. The essential extension of size compared to previous studies and the additional shape-optimisation of hcp and fcc clusters as well as truncated decahedra appears to be of high importance in the potential energy analysis. The best-optimised decahedra were confirmed to be the most favourable structure from 2000 to ~10⁵ atoms. Only in the short size interval, above N ∼10000 atoms, the best-optimised fcc clusters and simplest Marks' decahedra could alternate, while above N ∼14000 atoms does the shape-optimised hcp structure be proved to become more favourable for single crystal particles compared to the best-optimised fcc structure. Depending on shapes and sizes, decahedra and hcp clusters can alternate in the wide size interval above N ∼ 14000 atoms and presumably form the mixed abundances of clusters belonging to the both symmetries. Finally, the upper limit for stable MTPs was estimated to be about N ∼10⁵ atoms, while above only the hcp clusters are the most favourable.     

The energetics of mercury adsorption on Cu(100)

We have investigated the adsorption of mercury overlayers on Cu(100) by atom beam scattering, low energy electron diffraction and angle resolved photoemission. From our data we have calculated the isosteric heats in the adsorbed Hg layer on Cu(100) and compared these with results obtained for mercury on Fe(100), W(100) and Ni(100). We observe changes in the isosteric heat of adsorption that can be associated with the ordering of a c(2 × 2) Hg overlayer phase and the transition from a c(2 × 2) overlayer to a c(4 × 4) overlayer. The isosteric heat of adsorption is 0.50 ± 0.07 eV/atom (48 ± 7 kJ/mol) at zero coverage and reaches a maximum of 0.73 ± 0.04 eV/atom (70 ± 4 kJ/mol). From a combination of ABS and LEED, the structures of the two equilibrium ordered phases of Hg on Cu(100) have been identified, as well as the structures of several non-equilibrium phases.     

Experimental measurements of the energetics of surface reactions

Microcalorimetric measurements of the adsorption energies of well-defined surface species are reviewed, using selected examples mainly from our own group to demonstrate the types of information that can be achieved with this technique. The adsorption energies of molecules on single crystal transition metal surfaces to produce well-characterized molecular or dissociated adsorbates allow determination of the standard enthalpies of formation of key catalytic reaction intermediates. The adsorption energies for metal atoms during metal thin-film growth allow quantitative estimates of metal-substrate bond energies, metal film/substrate adhesion energies and the energetic costs associated with lattice mismatch during thin film growth. Results for several metals on MgO(1 0 0) reveal that they bind weakly to terrace sites. Metals from the right side of the periodic table also bind weakly to step and kink sites (although more strongly than on terraces), whereas alkali and alkaline earth metals bind very strongly to these defects. At 300 K, metals tend to form 2D or 3D clusters nucleated on MgO(1 0 0) defects, via a transiently adsorbed precursor (mobile adatoms on terraces). Calorimetric measurement of the energy of metal atoms in supported 3D metal nanoparticles as a function of particle size reveals a very strong size dependence below 6 nm diameter. Metal atoms also adsorb weakly on polymer surfaces and nucleate 3D metal particles, sometimes in kinetic competition with migration to and strong reaction with the more reactive, subsurface organic functional groups. Measurements of the energies for adsorbed proteins on calcium phosphate crystals, which have been structurally characterized by NMR, reveal extremely weak binding dominated by the entropy gained from release of organized water. These experimental measurements of the energies of well-defined adsorbates serve as benchmarks against which to compare theoretical computations for accuracy, thus enabling improvement upon quantum mechanical methods. Comparisons of calorimetric adsorption energies on single crystal surfaces with state-of-the-art DFT calculations show that the latter can often be in substantial (?20%) error.     

The g-factor of the Jπ=12+ isomeric state in188Hg

Using the reaction¹⁷⁵Lu(¹⁹F, 6n) theg-factor of the¹⁸⁸Hg isomeric state (J ^π=12⁺,T _1/2=135 ns) has been measured with the TDPAD method. The experimental value g=?0.168(10) supports the interpretation of an almost pure (vi13/2)^?2 configuration for this isomer.