Electronic states of neutral and ionized tetrahydrofuran studied by VUV spectroscopy and ab initio calculations

The electronic spectroscopy of isolated tetrahydrofuran (THF) in the gas phase has been investigated using high-resolution photoabsorption spectroscopy in the 5.8–10.6 eV with absolute cross-section measurements derived. In addition, an electron energy loss spectrum was recorded at 100 eV and 10° over the 5–11.4 eV range. The He(I) photoelectron spectrum was also collected to quantify ionisation energies in the 9–16.1 eV spectral region. These experiments are supported by the first high-level ab initio calculations performed on the excited states of the neutral molecule and on the ground state of the positive ion. The excellent agreement between the theoretical results and the measurements allows us to solve several discrepancies concerning the electronic state spectroscopy of THF. The present work reconsiders the question of the lowest energy conformers of the molecule and its population distribution at room temperature. Electronic supplementary material  Supplementary Online Material     

Ultra-low background measurements of decayed aerosol filters

Aerosol samples collected on filter media were analyzed using HPGe detectors employing varying background-reduction techniques in order to experimentally evaluate the opportunity to apply ultra-low background measurement methods to samples collected, for instance, by the Comprehensive Test Ban Treaty International Monitoring System (IMS). In this way, realistic estimates of the impact of low-background methodology on the sensitivity obtained in systems such as the IMS were assessed. The current detectability requirement of stations in the IMS is 30 μBq/m³ of air for ¹⁴⁰Ba, which would imply ~10⁶ fissions per daily sample. Importantly, this is for a fresh aerosol filter. One week of decay reduces the intrinsic background from radon daughters in the sample allowing much higher sensitivity measurement of relevant isotopes, including ¹³¹I. An experiment was conducted in which decayed filter samples were measured at a variety of underground locations using Ultra-Low Background (ULB) gamma spectroscopy technology. The impacts of the decay and ULB are discussed.     

Formation of Stripes and Slabs Near the Ferromagnetic Transition

We consider Ising models in d = 2 and d = 3 dimensions with nearest neighbor ferromagnetic and long-range antiferromagnetic interactions, the latter decaying as (distance)^?p , p > 2d, at large distances. If the strength J of the ferromagnetic interaction is larger than a critical value J _c , then the ground state is homogeneous. It has been conjectured that when J is smaller than but close to J _c , the ground state is periodic and striped, with stripes of constant width h = h(J), and h → ∞ as \({J\to J_c^-}\) . (In d = 3 stripes mean slabs, not columns.) Here we rigorously prove that, if we normalize the energy in such a way that the energy of the homogeneous state is zero, then the ratio e ₀(J)/e _S(J) tends to 1 as \({J\to J_c^-}\) , with e _S(J) being the energy per site of the optimal periodic striped/slabbed state and e ₀(J) the actual ground state energy per site of the system. Our proof comes with explicit bounds on the difference e ₀(J)?e _S(J) at small but positive J _c ?J, and also shows that in this parameter range the ground state is striped/slabbed in a certain sense: namely, if one looks at a randomly chosen window, of suitable size ? (very large compared to the optimal stripe size h(J)), one finds a striped/slabbed state with high probability.     

Structure and charge-state dependence of the gas-phase ionization energy of proteins

Photoionization of protein ions: The ionization energy of polyprotonated protein cations in the gas phase measured using VUV synchrotron radiation appears to be correlated with the charge state z of the protein and its tertiary structure. A simple electrostatic model accounts for the results and also shows predictive capabilities to derive a mean radius R(m) of the protein ion from the ionization energy, and vice versa.     

The Free Energy of the Quantum Heisenberg Ferromagnet at Large Spin

We consider the spin-S ferromagnetic Heisenberg model in three dimensions, in the absence of an external field. Spin wave theory suggests that in a suitable temperature regime the system behaves effectively as a system of non-interacting bosons (magnons). We prove this fact at the level of the specific free energy: if S???? and the inverse temperature ????0 in such a way that ??S stays constant, we rigorously show that the free energy per unit volume converges to the one suggested by spin wave theory. The proof is based on the localization of the system in small boxes and on upper and lower bounds on the local free energy, and it also provides explicit error bounds on the remainder.     

Ab initio and experimental study of the K-shell spectra of 2,5-dihydrofuran

The K-shell spectra of gaseous 2,5-dihydrofuran at the carbon and oxygen thresholds are reported for the first time. They have been measured using the inner-shell electron energy loss spectroscopy (ISEELS) method. Ab initio Configuration Interaction calculations have been carried out to assign the observed bands. The O1s spectrum is similar to that of tetrahydrofuran and the assignments of the bands are close to those obtained in the case of furan, excepting the furan first π* band. At the C1s edge, the spectrum differs from the furan case, because of the different chemical environment of one of the non-equivalent carbon atoms: due to the presence of hydrogen atoms out of the carbon–oxygen ring plane, several Rydberg core excited states have an important valence character, leading to large intensities in the experimental spectrum.