Economical quasi-Newton unitary optimization of electronic orbitals.

We present an efficient quasi-Newton orbital solver optimized to reduce the number of gradient evaluations and other computational steps of comparable cost. The solver optimizes orthogonal orbitals by sequences of unitary rotations generated by the (preconditioned) limited-memory Broyden-Fletcher-Goldfarb-Shanno (L-BFGS) algorithm equipped with trust-region step restriction. The low-rank structure of the L-BFGS inverse Hessian is exploited when solving the trust-region problem. The efficiency of the proposed "Quasi-Newton Unitary Optimization with Trust-Region" (QUOTR) solver is compared to that of the standard Roothaan-Hall approach accelerated by the Direct Inversion of Iterative Subspace (DIIS), and other exact and approximate Newton solvers for mean-field (Hartree-Fock and Kohn-Sham) problems.

Direct Determination of Optimal Real-Space Orbitals for Correlated Electronic Structure of Molecules.

We demonstrate how to determine numerically nearly exact orthonormal orbitals that are optimal for the evaluation of the energy of arbitrary (correlated) states of atoms and molecules by minimization of the energy Lagrangian. Orbitals are expressed in real space using a multiresolution spectral element basis that is refined adaptively to achieve the user-specified target precision while avoiding the ill-conditioning issues that plague AO basis set expansions traditionally used for correlated models of molecular electronic structure. For light atoms, the orbital solver, in conjunction with a variational electronic structure model [selected Configuration Interaction (CI)] provides energies of comparable precision to a state-of-the-art atomic CI solver. The computed electronic energies of atoms and molecules are significantly more accurate than the counterparts obtained with the orbital sets of the same rank expanded in Gaussian AO bases, and can be determined even when linear dependence issues preclude the use of the AO bases. It is feasible to optimize more than 100 fully correlated numerical orbitals on a single computer node, and significant room exists for additional improvement. These findings suggest that real-space orbital representations might be the preferred alternative to AO representations for high-end models of correlated electronic states of molecules and materials.

Actinide tetra-N-heterocyclic carbene 'sandwiches'.

Highly-symmetrical, thorium and uranium octakis-carbene 'sandwich' complexes have been prepared by 'sandwiching' the An(iv) cations between two anionic macrocyclic tetra-NHC ligands, one with sixteen atoms and the other with eighteen atoms. The complexes were characterized by a range of experimental methods and DFT calculations. X-ray crystallography confirms the geometry at the metal centre can be set by the size of the macrocyclic ring, leading to either square prismatic or square anti-prismatic shapes; the geometry of the latter is retained in solution, which also undergoes reversible, electrochemical one-electron oxidation or reduction for the uranium variant. DFT calculations reveal a frontier orbital picture that is similar to thorocene and uranocene, in which the NHC ligands show almost exclusively σ-donation to the metal without π-backbonding.

Establishing Cost-Effective Computational Models for the Prediction of Lanthanoid Binding in [Ln(NO3)]2+ (with Ln = La to Lu).

Evaluating the efficiency of predictive methods is critical to the processes of upscaling laboratory processes to full-scale operations on an industrial scale. With regard to separation of lanthanoids, there is a considerable motivation to optimize these processes because of immediate use in nuclear fuel cycle operations, nuclear forensics applications, and rare-earth metal recovery. Efficient predictive capabilities in Gibbs free energies of reaction are essential to optimize separations and ligand design for selective binding needed for various radiochemical applications such as nuclear fuel disposition and recycling of lanthanoid fission products into useful radioisotope products. Ligand design is essential for selective binding of lanthanoids, as separating contiguous lanthanoids is challenging because of the similar behavior these elements exhibit. Modeling including electronic structure calculations of lanthanoid-containing compounds is particularly challenging because of the associated computational cost encountered with the number of electrons correlated in these systems and relativistic considerations. This study evaluates the predictive capabilities of various ab initio methods in the calculation of Gibbs free energies of reaction for [Ln(NO3)]2+ compounds (with Ln = La to Lu), as nitrates are critical in traditional separation processes utilizing nitric acid. The composite methodologies evaluated predict Gibbs free energies of reaction for [Ln(NO3)]2+ compounds within 5 kcal mol-1 in most cases from the target method [CCSD(T)-FSII/cc-pwCV∞Z-DK3+SO] at a fraction of the computational cost.

Structural Analysis of the Complexation of Uranyl, Neptunyl, Plutonyl, and Americyl with Cyclic Imide Dioximes.

Knowledge-based design of extracting agents for selective binding of actinides is essential in stock-pile stewardship, environmental remediation, separations, and nuclear fuel disposal. Robust computational protocols are critical for in depth understanding of structural properties and to further advance the design of selective ligands. In particular, rapid radiochemical separations require predictive capabilities for binding in the gas phase. This study focuses on gas-phase binding preferences of cyclic imide dioximes to uranyl, neptunyl, plutonyl, and americyl. Structural properties, electron withdrawing effects, and their effects on binding preferences are studied with natural bond-order population analysis. The aromatic amidoximes are found to have a larger electron-donation effect than the aliphatic amidoximes. It is also found that plutonyl is more electron withdrawing than uranyl, neptunyl, and americyl when bound to the cyclic imide dioximes studied.

Structural Characteristics, Population Analysis, and Binding Energies of [An(NO3)]2+ (with An = Ac to Lr).

Efficient predictive capabilities are essential for the actinide series since regulatory constraints for radioactive work, associated costs needed for specialized facilities, and the short half-lives of many actinides present great challenges in laboratory settings. Improved predictive accuracy is advantageous for numerous applications including the optimization and design of separation agents for nuclear fuel and waste. One limitation of calculations in support of these applications is that the large variations observed from predictions obtained with currently available methods can make comparisons across studies uncertain. Benchmarking currently available computational methodologies is essential to establish reliable practices across the community to guarantee an accurate physical description of the systems studied. To understand the performance of a variety of common theoretical methods, a systematic analysis of differences observed in the prediction of structural characteristics, electron withdrawing effects, and binding energies of [An(NO3)]2+ (with An = Ac to Lr) in gas and aqueous phases is reported. Population analysis obtained with Mulliken and Löwdin reflect a large dependence on the level of theory of choice, whereas those obtained with natural bond orbital show larger consistency across methodologies. Predicted stability across the actinide series calculated with coupled cluster with perturbative doubles and triples at the triple ζ level is equivalent to the one obtained when extrapolated to the complete basis set limit. The ground state of [Fm(NO3)]2+ and [Md(NO3)]2+ is predicted to have an electronic structure corresponding to An III state in gas and An IV in aqueous phase, whereas the ground state of [An(NO3)]2+ (with An = Ac to Es, Lr) presents an electronic structure corresponding to An IV in the gas and aqueous phase. The compounds studied with No in gas and aqueous phase present a preferred No III state, and the Lr compounds did not follow trends predicted for the rest of the actinide series, as previously observed in studies regarding its unusual electronic structure relative to its position in the periodic table.

Effects of climatic variation on field metabolism and water relations of desert tortoises.

We used the doubly labeled water method to measure the field metabolic rates (FMRs, in kJ kg-1 day-1) and water flux rates (WIRs, in ml H2O kg-1 day-1) of adult desert tortoises (Gopherus agassizii) in three parts of the Mojave Desert in California over a 3.5-year period, in order to develop insights into the physiological responses of this threatened species to climate variation among sites and years. FMR, WIR, and the water economy index (WEI, in ml H2O kJ-1, an indicator of drinking of free water) differed extensively among seasons, among study sites, between sexes, and among years. In high-rainfall years, males had higher FMRs than females. Average daily rates of energy and water use by desert tortoises were extraordinarily variable: 28-fold differences in FMR and 237-fold differences in WIR were measured. Some of this variation was due to seasonal conditions, with rates being low during cold winter months and higher in the warm seasons. However, much of the variation was due to responses to year-to-year variation in rainfall. Annual spring peaks in FMR and WIR were higher in wet years than in drought years. Site differences in seasonal patterns were apparently due to geographic differences in rainfall patterns (more summer rain at eastern Mojave sites). In spring 1992, during an El Niño (ENSO) event, the WEI was greater than the maximal value obtainable from consuming succulent vegetation, indicating copious drinking of rainwater at that time. The physiological and behavioral flexibility of desert tortoises, evident in individuals living at all three study sites, appears central to their ability to survive droughts and benefit from periods of resource abundance. The strong effects of the El Niño (ENSO) weather pattern on tortoise physiology, reproduction, and survival elucidated in this and other studies suggest that local manifestations of global climate events could have a long-term influence on the tortoise populations in the Mojave Desert.

Physiological and behavioral variation in estivation among mud turtles (Kinosternon spp.).

Kinosternid mud turtles, a primarily aquatic group, exhibit variable degrees of terrestrial activity in the Sonoran and Chihuahuan Deserts. We compared behavioral and physiological responses to dry conditions in four populations representing three species, Kinosternon sonoriense, Kinosternon flavescens, and Kinosternon hirtipes. All four groups were subjected to simulated dry season conditions in the laboratory, during which activity was monitored and physiological responses (blood chemistry and rates of resting metabolism and evaporative water loss) were measured. Kinosternon flavescens and K. hirtipes represented extremes in apparent ability to estivate, based on activity and rate of increase of plasma osmolality. Two populations of K. sonoriense exhibited intraspecific differences in behavioral and physiological measures that were related to extant environmental conditions. Large numbers of K. sonoriense from Arizona and K. hirtipes, the poorest estivators, had to be rehydrated after only 30 d out of water. Kinosteron flavescens had the lowest metabolic rates, but no evidence of metabolic depression during dehydration was found for any of the four populations. We conclude that the differences in capacity for estivation among populations are primarily linked to variable behavioral responses to dry conditions, though high rates of evaporative water loss in K. hirtipes represent a probable physiological constraint.

Acute and persistent effects of pre- and posthatching thermal environments on growth and metabolism in the red-eared slider turtle, Trachemys scripta elegans.

Many ectotherms possess the capacity to survive a wide range of thermal conditions. Long-term exposure to temperature can induce acclimational and/or organizational effects, and the developmental stage at which temperature exposure occurs may affect the type, degree, and persistence of these effects. We incubated red-eared slider turtle embryos at three different constant temperatures (T(inc); 26.5, 28.5, 30.5°C), then divided the resulting hatchlings between two water temperatures (T(water); 25, 30°C). We calculated growth rates to assess the short- and long-term effects of thermal experience on this metabolically costly process. We also measured resting metabolic rate (RMR) at three body temperatures (T(body;) 26.5, 28.5, 30.5°C) shortly after hatching and 6 months posthatching to characterize the degree and persistence of acclimation to T(inc) and T(water) . Hatchling RMRs were affected by T(body) and T(inc) , and fit a pattern consistent with positive but incomplete metabolic compensation to T(inc) . Average growth rates over the first 11 weeks posthatching were strongly affected by T(water) but only marginally influenced by T(inc) , and only at T(water) = 30°C. Six-month RMRs exhibited strong acclimation to T(water) consistent with positive metabolic compensation. However, within each T(water) treatment, RMR fit patterns indicative of inverse metabolic compensation to T(inc) , opposite of the pattern observed in hatchlings. Average growth rates calculated over 6 months continued to show a strong effect of T(water) , and the previously weak effect of T(inc) observed within the 30°C T(water) treatment became more pronounced. Our results suggest that metabolic compensation was reversible regardless of the life stage during which exposure occurred, and therefore is more appropriately considered acclimational than organizational.

Bone disease in thalassemia: a frequent and still unresolved problem.

Adults with beta thalassemia major frequently have low BMD, fractures, and bone pain. The purpose of this study was to determine the prevalence of low BMD, fractures, and bone pain in all thalassemia syndromes in childhood, adolescence, and adulthood, associations of BMD with fractures and bone pain, and etiology of bone disease in thalassemia. Patients of all thalassemia syndromes in the Thalassemia Clinical Research Network, > or =6 yr of age, with no preexisting medical condition affecting bone mass or requiring steroids, participated. We measured spine and femur BMD and whole body BMC by DXA and assessed vertebral abnormalities by morphometric X-ray absorptiometry (MXA). Medical history by interview and review of medical records, physical examinations, and blood and urine collections were performed. Three hundred sixty-one subjects, 49% male, with a mean age of 23.2 yr (range, 6.1-75 yr), were studied. Spine and femur BMD Z-scores < -2 occurred in 46% and 25% of participants, respectively. Greater age, lower weight, hypogonadism, and increased bone turnover were strong independent predictors of low bone mass regardless of thalassemia syndrome. Peak bone mass was suboptimal. Thirty-six percent of patients had a history of fractures, and 34% reported bone pain. BMD was negatively associated with fractures but not with bone pain. Nine percent of participants had uniformly decreased height of several vertebrae by MXA, which was associated with the use of iron chelator deferoxamine before 6 yr of age. In patients with thalassemia, low BMD and fractures occur frequently and independently of the particular syndrome. Peak bone mass is suboptimal. Low BMD is associated with hypogonadism, increased bone turnover, and an increased risk for fractures.

Energy metabolism of male and female tarantulas (Aphonopelma anax) during locomotion.

We examined aerobic performance traits in male and female tarantulas (Aphonopelma anax). Reproductive fitness in these males relies heavily on locomotory searching to locate receptive females, which are fossorial and sedentary. Because of this dimorphism in life history, we predicted that selection in males would enhance their ability to sustain high levels of aerobic metabolism (compared with females) to support increased locomotory activity during the mating season. Rates of carbon dioxide production were measured in an enclosed variable-speed treadmill. Steady-state rates of carbon dioxide production increased linearly within the range of sustainable aerobic speeds for both males and females. Although there was substantial variation in physiological performance traits among individuals, there were no detectable intersexual differences in maximal rates of carbon dioxide production, maximal aerobic speed, minimum transport or factorial scope.