Best optimized one-electron wave-functions. II. Isoelectronic series of Li,Be, B,and C

A study of selected electronic properties for isoelectronic series of Li, Be, B, and C has been presented. The study is based on the recently developed procedure of optimization of atomic spin-orbitals.     

Spin contamination for Hartree-Fock, optimized effective potential, and density functional approximations

In an earlier paper [S. Thanos and A. K. Theophilou J. Chem. Phys. 124, 204109 (2006)], we found an explicit formula for the expansion of a Slater determinant |Phi(M)> in terms of eigenstates of S(2). In this paper, we use the same formula to determine the spin contamination S(con) of the unrestricted single determinant approximations, i.e., Hartree-Fock, optimized effective potential, and density functional theory. We derived an expression which gives S(con) in terms of the overlap of the spatial parts of the spin up and spin down "corresponding" orbitals. It was found that S(con) does not depend on M, the eigenvalue of S(z), at least for the lower order approximations, i.e., when || is large. In this case, the predominant coefficient of the expansion assumes its maximum value when S=M. However, for the class of solutions that || is small, the spin L of the largest coefficient increases with the number of unpaired electrons. We also derived the explicit form of the expansion states.     

XPS,AES, and AFM as tools for study of optimized plasma functionalization

The plasma-based surface modification of polymer materials with desirable bulk properties is a useful way to obtain polymers with tailor-made surface properties. This is necessary because the surface properties of most engineering polymers in use today are less then optimum for many applications. New functionalities such as biocompatibility, adhesion, special functional groups as well as lubricative, friction and wear-and-tear properties are demanded. By optimization of the process parameters during a low pressure plasma treatment, most of these requirements can be fulfilled. A specific functionalization with, e.g., carboxyl, amino, epoxy or hydroxyl groups as well as the generation of ultra thin layers with those functionalities is possible. The most challenging problem is not only to find parameters which do not lead to a fragmentation of the monomeric structure, but moreover the adhesion of the thin films to the substrates must overcome a stability test without delamination. To optimize plasma processes, with their great variety of parameters influencing the obtained surface properties, several surface analytical techniques are indispensable. XPS, AES as well as AFM are helpful tools to characterize the modified sample surfaces and consequently optimize the set of parameters for the glow discharge treatment. With XPS the retention of the monomer structure can be controlled. AES depth profiling clarifies the elemental composition of gradient layers, necessary for a good adhesion of scratch-resistant coatings. AFM visualizes the surface morphology which is important for, e.g., the friction properties of plasma-coated substrates.     

An optimized protocol for anthraquinones isolation from Rhamnus frangula L.

Different from works described in the literature, which use expansive analytical methods to separation of anthraquinones derivatives (AQs), this communication reported a simple and inexpensive methodology to get them. In this way, the expensive commercial AQs: Chrysophanol, physcione and emodine were extracted from plant material (Rhamnus frangula L.) and isolated by classical column chromatography technique under optimised binary mobile phase gradients (CHCl₃ : AcOEt(a), a = 1 to 5%) in excellent yields.     

Matrix-shimmed ion cyclotron resonance ion trap simultaneously optimized for excitation, detection, quadrupolar axialization, and trapping

A different symmetry is required to optimize each of the three most common Fourier transform ion cyclotron resonance mass spectrometry (FT-ICR MS) electric potentials in a Penning (ICR) ion trap: one-dimensional dipolar ac for excitation (or detection), two-dimensional azimuthal quadrupolar ac excitation for ion axialization, and three-dimensional axial quadrupolar dc potential for ion axial confinement (trapping). Since no single trap shape simultaneously optimizes all three potentials, many trap configurations have been proposed to optimize the tradeoffs between the three requirements for a particular experiment. A more general approach is to divide each electrode into small segments and then apply the appropriate potential to each segment. Here, we extend segmentation to its logical extreme, by constructing a “matrix-shimmed” trap consisting of a cubic trap, with each side divided into a 5 × 5 grid of electrodes for a total of 150 electrodes. Theoretically, only 48 independent voltages need be applied to these 150 electrodes to generate all three desired electric potential fields simultaneously. In practice, it is more convenient to employ 63 independent voltages due to construction constraints. Resistive networks generate the potentials required for optimal quadrupolar trapping and quadrupolar excitation. To avoid resistive loss of excitation amplitude and detected signal, dipolar excitation/detection voltages are generated with a capacitive network. Theoretical Simion 6. 0 simulations confirm the achievement of near-ideal potentials of all three types simultaneously. From a proof-of-principle working model, several experimental benefits are demonstrated, and proposed future improvements are discussed.     

Uniform quality gaussian basis sets for molecular calculations. III. Charge optimized basis sets

Gradient optimized constrained (2s ≠ 2p) and unconstrained (2s ≠ 2p) Gaussian 3G basis sets are reported for the first-row atoms and ions X^O, for Q = ?2 to +4. Analytic equations have been fitted to the logarithm of the exponents as a function of the nuclear charge Z and formal charge Q. Consequently only two parameters Z and Q have to be specified in order to completely define a basis set.     

Localized optimized orbitals, coupled cluster theory, and chiroptical response properties

The impact of orbital localization on the efficiency and accuracy of the optimized-orbital coupled cluster model is examined for the prediction of chiroptical properties, in particular optical rotation. The specific rotations of several test cases-(P)-[4]triangulane, (S)-1-phenylethanol, and chiral conformers of 1-fluoropentane, heptane, and nonane-were computed using an approach in which localization is enforced throughout the orbital optimization and subsequent linear response computation. This method provides a robust local-correlation scheme for future production-level implementation. Although the cross-over point between the canonical and localized coupled cluster approach lies at larger molecules than for ground-state energies, the scheme presented should still provide reduced scaling sufficient to investigate much larger molecules than are presently accessible.     

Uniform quality gaussian basis sets for molecular calculations. IV. Gradient and charged optimized basis sets for CH4

Comparison of the molecular Q-optimized and molecular gradient optimized carbon basis sets for CH 4 showed that molecular Q optimization is an excellent substitute to the more expensive molecular gradient optimization. The parameter Q of the Q optimization is related to the population (i.e., net charge) on the atom.     

Planar artificial biomembranes optimized for biochemical assay

Langmuir-Blodgett monolayer and planar bilayer lipid membrane (BLM) experiments are used to study the relative significance of dipolar potential and packing/fluidity in the control of the permeability of phospholipid/steroid BLMs to potassium ion. Practical chemical construction of BLMs designed to achieve particular dipolar potential and packing/fluidity characteristics are described. The ability to modify selectively the salient physical properties of BLMs allows optimization of the ion permeability and receptor activity of the membrane. The use of BLMs to quantify drug response and receptor activity is illustrated by examples involving valinomycin, phloretin, concanavalin A and auxin receptor.     

An optimized molecular potential for carbon dioxide

An optimized molecular potential model for carbon dioxide is presented in this paper. Utilizing the established techniques of molecular-dynamics and histogram reweighting grand canonical Monte Carlo simulations, this model is demonstrated to show excellent predictability for thermodynamic, transport, and liquid structural properties in a wide temperature-pressure range with remarkable accuracies. The average deviations of this new model from experimental data for the saturated liquid densities, vapor densities, vapor pressures, and heats of vaporization are around 0.1%, 2.3%, 0.7%, and 1.9%, respectively. The calculated critical point is almost pinpointed by the new model. The experimental radial distribution functions ranging from 240.0 to 473.0 K are well reproduced as compared to neutron-diffraction measurements. The predicted self-diffusion coefficients are in good agreement with the nuclear-magnetic-resonance measurements. The previously published potential models for CO2 are also systematically evaluated, and our proposed new model is found to be superior to the previous models in general.