Mass Transfer in High Performance Liquid Chromatography

10

Self-Consistent Electron-Nucleus Cusp Correction for Molecular Orbitals

We describe a method for imposing the correct electron-nucleus (e-n) cusp in molecular orbitals expanded as a linear combination of (cuspless) Gaussian basis functions. Enforcing the e-n cusp in trial wave functions is an important asset in quantum Monte Carlo calculations as it significantly reduces the variance of the local energy during the Monte Carlo sampling. In the method presented here, the Gaussian basis set is augmented with a small number of Slater basis functions. Note that, unlike other e-n cusp correction schemes, the presence of the Slater function is not limited to the vicinity of the nuclei. Both the coefficients of these cuspless Gaussian and cusp-correcting Slater basis functions may be self-consistently optimized by diagonalization of an orbital-dependent effective Fock operator. Illustrative examples are reported for atoms (\ce{H}, \ce{He} and \ce{Ne}) as well as for a small molecular system (\ce{BeH2}). For the simple case of the \ce{He} atom, we observe that, with respect to the cuspless version, the variance is reduced by one order of magnitude by applying our cusp-corrected scheme.Comment: 23 pages, 5 figure

Planning and Estimation of Operations Support Requirements

Life Cycle Cost (LCC) estimates during the proposal and early design phases, as well as project replans during the development phase, are heavily focused on hardware development schedules and costs. Operations (phase E) costs are typically small compared to the spacecraft development and test costs. This, combined with the long lead time for realizing operations costs, can lead to de-emphasizing estimation of operations support requirements during proposal, early design, and replan cost exercises. The Discovery and New Frontiers (D&NF) programs comprise small, cost-capped missions supporting scientific exploration of the solar system. Any LCC growth can directly impact the programs' ability to fund new missions, and even moderate yearly underestimates of the operations costs can present significant LCC impacts for deep space missions with long operational durations. The National Aeronautics and Space Administration (NASA) D&NF Program Office at Marshall Space Flight Center (MSFC) recently studied cost overruns and schedule delays for 5 missions. The goal was to identify the underlying causes for the overruns and delays, and to develop practical mitigations to assist the D&NF projects in identifying potential risks and controlling the associated impacts to proposed mission costs and schedules. The study found that 4 out of the 5 missions studied had significant overruns at or after launch due to underestimation of the complexity and supporting requirements for operations activities; the fifth mission had not launched at the time of the mission. The drivers behind these overruns include overly optimistic assumptions regarding the savings resulting from the use of heritage technology, late development of operations requirements, inadequate planning for sustaining engineering and the special requirements of long duration missions (e.g., knowledge retention and hardware/software refresh), and delayed completion of ground system development work. This paper updates the D&NF LCC study, looking at the operations (phase E) cost drivers in more detail and extending the study to include 2 additional missions and identifies areas for increased emphasis by project management in order to improve the fidelity of operations estimates

Spectroscopy and Dynamics of the Predissociated, Quasi-linear S2 State of Chlorocarbene

In this work, we report on the spectroscopy and dynamics of the quasi-linear S2 state of chlorocarbene, CHCl, and its deuterated isotopologue using optical-optical double resonance (OODR) spectroscopy through selected rovibronic levels of the S1 state. This study, which represents the first observation of the S2 state in CHCl, builds upon our recent examination of the corresponding state in CHF, where pronounced mode specificity was observed in the dynamics, with predissociation rates larger for levels containing bending excitation. In the present work, a total of 14 S2 state vibrational levels with angular momentum ℓ = 1 were observed for CHCl, and 34 levels for CDCl. The range of ℓ in this case was restricted by the pronounced Renner-Teller effect in the low-lying S1 levels, which severely reduces the fluorescence lifetime for levels with Ka \u3e 0. Nonetheless, by exploiting different intermediate S1 levels, we observed progressions involving all three fundamental vibrations. For levels with long predissociation lifetimes, rotational constants were determined by measuring spectra through different intermediate J levels of the S1 state. Plots of the predissociation linewidth (lifetime) vs. energy for various S2 levels show an abrupt onset, which lies near the calculated threshold for elimination to form C(3P) + HCl on the triplet surface. Our experimental results are compared with a series of high level ab initio calculations, which included the use of a dynamically weighted full-valence CASSCF procedure, focusing maximum weight on the state of interest (the singlet and triplet states were computed separately). This was used as the reference for subsequent Davidson-corrected MRCI(+Q) calculations. These calculations reveal the presence of multiple conical intersections in the singlet manifold

Protein and alkaloid patterns of the floral nectar in some solanaceous species

The family Solanaceae includes several melliferous plants, which tend to produce copious amounts of nectar. Floral nectar is a chemically complex aqueous solution, dominated by sugars, but minor components such as amino acids, proteins, flavonoids and alkaloids are present as well. This study aimed at analysing the protein and alkaloid profile of the nectar in seven solanaceous species. Proteins were examined with SDS-PAGE and alkaloids were analyzed with HPLC. The investigation of protein profile revealed significant differences in nectar-protein patterns not only between different plant genera, but also between the three Nicotiana species investigated. SDS-PAGE suggested the presence of several Nectarin proteins with antimicrobial activity in Nicotiana species. The nectar of all tobacco species contained the alkaloid nicotine, N. tabacum having the highest nicotine content. The nectar of Brugmansia suaveolens, Datura stramonium, Hyoscyamus niger and Lycium barbarum contained scopolamine, the highest content of which was measured in B. suaveolens. The alkaloid concentrations in the nectars of most solanaceous species investigated can cause deterrence in honeybees, and the nectar of N. rustica and N. tabacum can be considered toxic for honeybees

Heritage and Advanced Technology Systems Engineering Lessons Learned from NASA Space Missions

Use of heritage and new technology is necessary/enabling to implementing small, low cost missions, yet overruns decrease the ability to sustain future mission flight rates The majority of the cost growth drivers seen in the D&NF study were embedded early during formulation phase and later realized during the development and I&T phases Cost drivers can be avoided or significantly decreased by project management and SE emphasis on early identification of risks and realistic analyses SE processes that emphasize an assessment of technology within the mission system to identify technical issues in the design or operational use of the technology. Realistic assessment of new and heritage spacecraft technology assumptions , identification of risks and mitigation strategies. Realistic estimates of effort required to inherit existing or qualify new technology, identification of risks to estimates and develop mitigation strategies. Allocation of project reserves for risk-based mitigation strategies of each individual area of heritage or new technology. Careful tailoring of inheritance processes to ensure due diligence

The Virial Theorem and Covalent Bonding

A long-held view of the origin of covalent binding is based on the notion that electrostatic forces determine the stability of a system of charged particles and that, therefore, potential energy changes drive the stabilization of molecules. A key argument advanced for this conjecture is the rigorous validity of the virial theorem. Rigorous in-depth analyses have however shown that the energy lowering of covalent bonding is due to the wave mechanical drive of electrons to lower their kinetic energy through expansion. Since the virial theorem applies only to systems with Coulombic interaction potentials, its relevance as a foundation of the electrostatic view is tested here by calculations on analogues of the molecules H2+ and H2, where all 1/r interaction potentials are replaced by Gaussian-type potentials that yield one-electron “atoms” with realistic stability ranges. The virial theorem does not hold in these systems, but covalent bonds are found to form nonetheless, and the wave mechanical bonding analysis yields analogous results as in the case of the Coulombic potentials. Notably, the key driving feature is again the electron delocalization that lowers the interatomic kinetic energy component. A detailed discussion of the role of the virial theorem in the context of covalent binding is given