The electronic structure of thorium monoxide: Ligand field assignment of states in the range 0-5 eV.

Configuration interaction ligand field theory (CI LFT) calculations of the electronic energy levels of ThO were performed by treating the molecular electronic states as Th 2+ free-ion levels perturbed by the ligand field of O2- . Twenty nine experimentally characterized ThO v = 0 energy levels, together with the energy difference between the v = 0 levels of the Y and W states were fitted using a CI LFT model that included Th 2+ 7s 2 , 6d7s, 6d2 , 7s7p, 6d7p, 5f7s, and 7p2 configurations. Predictions from these calculations were used to provide tentative assignments for 171 out of 250 ThO band heads listed by Gatterer et al. ["Molecular Spectra of Metallic Oxides", Specola Vaticana (1957)]. Term energies for 30 electronic states have been determined based on these assignments. Subsequently, the CI LFT model was refined by fitting to a set of 59 electronic term energies. The inclusion of CI effects together with integer valence, atomic-in-molecule, ionic bonding ideas reveals atomic energy level patterns that are multiply replicated in the molecular energy level patterns of six Th 2+ O2- atomic ion configurations (6d7s, 6d2 , 7s7p, 6d7p, 5f7s, and 7p2 ) revealing the underlying atomic ion structure that gives rise to the complex and seemingly erratic unassigned bands reported in the Vatican Atlas. © 2018 Wiley Periodicals, Inc.

Molecular identification of individual nano-objects.

Secondary ion mass spectrometry (SIMS) run in the event-by-event bombardment/detection mode provides a unique ability to obtain molecular information from single nano-objects, since assays are based on secondary ion coemission from single impacts. The characterization of individual nano-objects is demonstrated with negatively charged polymer spheres that are attracted to and retained by nanoalumina whiskers. The whiskers, 2 nm in diameter and approximately 250 nm in length, are grafted to a microglass fiber with an average diameter of approximately 0.6 microm and several millimeters long. The spheres are monodisperse polystyrene nanoparticles (30 nm diameter). Massive Au projectiles, specifically 136 keV Au(400)(4+), were utilized to bombard analyte surfaces due to its high efficiency for producing multi-ion emission identified by time-of-flight mass spectrometry. Our results show that this mode of mass spectrometry can provide information on the nature, size, relative location, and abundance of nano-objects in the field of view. The key to characterizing nanodomains is to monitor the coincidental secondary ion emission from the nanovolume perturbed by single projectile impacts.

Characterization of individual nano-objects by secondary ion mass spectrometry.

We present secondary ion mass spectrometry (SIMS) data obtained from the bombardment of a novel nanomaterial with a suite of projectiles: Au1+, Au3+, Au9+, and Au400(4+). These are the first experiments where free-standing nano-objects were bombarded with kiloelectronvolt projectiles of atomic to nanoparticle size (Au400(4+)). The objects are aluminum monohydrate nanowhiskers, identified as crystalline boehmite (AlOOH) using X-ray diffraction. The nanoalumina is bonded to a microglass fiber that serves as a scaffold. The largest projectile, Au400(4+), has a diameter of approximately 2 nm, comparable to the nominal diameter of the nanowhiskers. There are notable differences in secondary ion (SI) response from sample volumes too small for full projectile energy deposition. The whisker spectra are dominated by small clusters--the most abundant species being AlO- and AlO2-. Bulk samples have larger yields for AlO2- than AlO-, whereas this trend is reversed in the whisker samples. Bulk samples give similar abundances of large SI cluster families [(Al2O3)(n)AlO2]- and [(Al2O3)(n)OH]-, whereas the whisker samples give an order of magnitude lower yield of these SIs. Given the nature of our experiments, i.e., the event-by-event bombardment/detection mode, we are uniquely able to obtain information from SIs emitted from single-projectile impacts. As such, effective yields were calculated in order to determine quantitative differences between the nano-objects and bulk samples.

Probing the electronic structure of UO+ with high-resolution photoelectron spectroscopy.

The pulsed field ionization-zero kinetic energy photoelectron technique has been used to observe the low-lying energy levels of UO+. Rotationally resolved spectra were recorded for the ground state and the first nine electronically excited states. Extensive vibrational progressions were characterized. Omega+ assignments were unambiguously determined from the first rotational lines identified in each vibronic band. Term energies, vibrational frequencies, and anharmonicity constants for low-lying energy levels of UO+ are reported. In addition, accurate values for the ionization energies for UO [48,643.8(2) cm(-1)] and U [49,957.6(2) cm(-1)] were determined. The pattern of low-lying electronic states for UO+ indicates that they originate from the U3+(5f3)O2- configuration, where the uranium ion-centered interactions between the 5f electrons are significantly stronger than interactions with the intramolecular electric field. The latter lifts the degeneracy of U3+ ion-core states, but the atomic angular momentum quantum numbers remain reasonably well defined.

Ionization energy measurements and electronic spectra for ThO.

The ionization energy (IE) for ThO has been determined using photoionization efficiency and mass-analyzed threshold ionization measurements. An IE of 6.6038(12) eV was obtained, which was appreciably higher than the result from previous appearance potential measurements [6.1(1) eV]. The revised IE is 0.3 eV greater than that of atomic Th, indicating that neutral ThO is more tightly bound than ThO(+). The one-color two-photon resonant ionization spectrum of ThO was examined in the range of 315-370 nm. Rotationally resolved bands were recorded for three new electronic states (designated as E('),F('), and G(')). In addition, transitions to the A(')(v=1,2,3) levels and the N(v=2) level were observed for the first time. Ligand field theory predictions [L. A. Kaledin, J. E. McCord, and M. C. Heaven, J. Mol. Spectrosc. 164, 27 (1994)] were used to propose configurational assignments for 20 electronically excited states.

Electronic spectroscopy and ionization potential of UO2 in the gas phase.

The electronic spectroscopy of UO(2) has been examined using multiphoton ionization with mass-selected detection of the UO(2) (+) ions. Supersonic jet cooling was used to reduce the spectral congestion. Twenty-two vibronic bands of neutral UO(2) were observed in the range from 17,400 to 32,000 cm(-1). These bands originated from the U(5fphi(u)7ssigma(g))O(2) X (3)Phi(2u) and (3)Phi(3u) states. The stronger band systems are attributed to metal-centered 7p<--7s transitions. Threshold ionization measurements were used to determine the ionization potentials of UO and UO(2). These were found to be higher than the values obtained previously from electron impact measurements but in agreement with the results of recent theoretical calculations.

Osteoblast function on nanophase alumina materials: Influence of chemistry, phase, and topography.

Alumina is a material that has been used in both dental and orthopedic applications. It is with these uses in mind that osteoblast (bone-forming cell) function on alumina of varying particulate size, chemistry, and phase was tested in order to determine what formulation might be the most beneficial for bone regeneration. Specifically, in vitro osteoblast adhesion, proliferation, intracellular alkaline phosphatase activity, and calcium deposition was observed on delta-phase nanospherical, alpha-phase conventional spherical, and boehmite nanofiber alumina. Results showed for the first time increased osteoblast functions on the nanofiber alumina. Specifically, a 16% increase in osteoblast adhesion over nanophase spherical alumina and a 97% increase over conventional spherical alumina were found for nanofiber alumina after 2 h. A 29% increase in cell number after 5 days and up to a 57% greater amount of calcium was found on the surface of the nanofiber alumina compared with other alumina surfaces. Some of the possible explanations for such enhanced osteoblast behavior on nanofiber alumina may be attributed to chemistry, crystalline phase, and topography. Increased osteoblast function on nanofiber alumina suggests that it may be an ideal material for use in orthopedic and dental applications.

Accurate ionization potentials for UO and UO2: a rigorous test of relativistic quantum chemistry calculations.

Accurate ionization potential (IP) measurements provide essential thermodynamic information and benchmark data that can be used to evaluate the validity of electronic structure models. Calculations of the first IP of UO2 using relativistic methods consistently predict values that are approximately 0.7 eV higher than the accepted experimental value. The present measurements validate the theoretical calculations and show that the previous determinations corresponded to the ionization of thermally excited molecules. Similarly, new measurements of the IP for UO show that the currently accepted value is too low by 0.4 eV.