Crystal Coulomb energies: I. Organic donor-acceptor complexes--a review. II. Classical Ewald calculations of the Coulomb binding energy of four donor-acceptor crystals and Wurster's blue perchlorate. III. A rapid-convergence quantum-mechanical formalism for crystal electronic energies

Chapter I

Theories for organic donor-acceptor (DA) complexes in solution and in the solid state are reviewed, and compared with the available experimental data. As shown by McConnell et al. (Proc. Natl. Acad. Sci. U.S., 53, 46-50 (1965)), the DA crystals fall into two classes, the holoionic class with a fully or almost fully ionic ground state, and the nonionic class with little or no ionic character. If the total lattice binding energy 2ε₁ (per DA pair) gained in ionizing a DA lattice exceeds the cost 2ε_o of ionizing each DA pair, ε₁ + ε_o less than 0, then the lattice is holoionic. The charge-transfer (CT) band in crystals and in solution can be explained, following Mulliken, by a second-order mixing of states, or by any theory that makes the CT transition strongly allowed, and yet due to a small change in the ground state of the non-interacting components D and A (or D⁺ and A^-). The magnetic properties of the DA crystals are discussed.

Chapter II

A computer program, EWALD, was written to calculate by the Ewald fast-convergence method the crystal Coulomb binding energy E_C due to classical monopole-monopole interactions for crystals of any symmetry. The precision of E_C values obtained is high: the uncertainties, estimated by the effect on E_C of changing the Ewald convergence parameter η, ranged from ± 0.00002 eV to ± 0.01 eV in the worst case. The charge distribution for organic ions was idealized as fractional point charges localized at the crystallographic atomic positions: these charges were chosen from available theoretical and experimental estimates. The uncertainty in E_C due to different charge distribution models is typically ± 0.1 eV (± 3%): thus, even the simple Hückel model can give decent results.

E_C for Wurster's Blue Perchl orate is -4.1 eV/molecule: the crystal is stable under the binding provided by direct Coulomb interactions. E_C for N-Methylphenazinium Tetracyanoquino- dimethanide is 0.1 eV: exchange Coulomb interactions, which cannot be estimated classically, must provide the necessary binding.

EWALD was also used to test the McConnell classification of DA crystals. For the holoionic (1:1)-(N,N,N',N'-Tetramethyl-para- phenylenediamine: 7,7,8,8-Tetracyanoquinodimethan) E_C = -4.0 eV while 2ε_o = 4.6₅ eV: clearly, exchange forces must provide the balance. For the holoionic (1:1)-(N,N,N',N'-Tetramethyl-para- phenylenediamine:para-Chloranil) E_C = -4.4 eV, while 2ε_o = 5.0 eV: again EC falls short of 2ε₁. As a Gedankenexperiment, two nonionic crystals were assumed to be ionized: for (1:1)-(Hexamethyl- benzene:para-Chloranil) E_C = -4.5 eV, 2ε_o = 6.6 eV; for (1:1)- (Napthalene:Tetracyanoethylene) E_C = -4.3 eV, 2ε_o = 6.5 eV. Thus, exchange energies in these nonionic crystals must not exceed 1 eV.

Chapter III

A rapid-convergence quantum-mechanical formalism is derived to calculate the electronic energy of an arbitrary molecular (or molecular-ion) crystal: this provides estimates of crystal binding energies which include the exchange Coulomb inter- actions. Previously obtained LCAO-MO wavefunctions for the isolated molecule(s) ("unit cell spin-orbitals") provide the starting-point. Bloch's theorem is used to construct "crystal spin-orbitals". Overlap between the unit cell orbitals localized in different unit cells is neglected, or is eliminated by Löwdin orthogonalization. Then simple formulas for the total kinetic energy Q^(XT)_λ, nuclear attraction [λ/λ]^XT, direct Coulomb [λλ/λ'λ']^XT and exchange Coulomb [λλ'/λ'λ]^XT integrals are obtained, and direct-space brute-force expansions in atomic wavefunctions are given. Fourier series are obtained for [λ/λ]^XT, [λλ/λ'λ']^XT, and [λλ/λ'λ]^XT with the help of the convolution theorem; the Fourier coefficients require the evaluation of Silverstone's two-center Fourier transform integrals. If the short-range interactions are calculated by brute-force integrations in direct space, and the long-range effects are summed in Fourier space, then rapid convergence is possible for [λ/λ]^XT, [λλ/λ'λ']^XT and [λλ'/λ'λ]^XT. This is achieved, as in the Ewald method, by modifying each atomic wavefunction by a "Gaussian convergence acceleration factor", and evaluating separately in direct and in Fourier space appropriate portions of [λ/λ]^XT, etc., where some of the portions contain the Gaussian factor.

Topic 1. Some steric-height features of the water off the Pacific coast of Canada; Topic 2. Possible warming of the water at station P in the northeast Pacific during 1956-1984 [abstract]

TOPIC 1: In terms of seasonal scale, temperature effect dominates the annual change of steric height in the open ocean whereas salinity effect controls it along the continental shelf. Large portion of the annual change of height relative to the 1000-db surface is contained in the upper 100m layer. However, in interannual scale large anomalies of steric height in the open ocean, are more often than not, caused by halosteric rather than thermosteric effect. At least in the open ocean the heights are almost totally determined by the behavior of deep water. Their interannual variability appears to be related to the cumulative effect of Eckman pumping. TOPIC 2: There is a "trend" that over the past 28 years the water at Station P has warmed. Least-square analysis indicates that this warming may be significant but shortening of the time-series data by approximately 10 years fails to show that this is the case. These "trends" have to be interpreted with care. The warming may be "apparent" in that it is not indicated clearly in the deep isopynal surfaces which, during the above period, have deepened. Thus warming at the isobaric surfaces may be the effect of the downward migration of the isopynal surfaces.

In search of climate effects on Atlantic Croaker (Micropogonias undulatus) stock off the U.S. Atlantic coast with Bayesian state-space biomass dynamic models

Atlantic Croaker (Micropogonias undulatus) production dynamics along the U.S. Atlantic coast are regulated by fishing and winter water temperature. Stakeholders for this resource have recommended investigating the effects of climate covariates in assessment models. This study used state-space biomass dynamic models without (model 1) and with (model 2) the minimum winter estuarine temperature (MWET) to examine MWET effects on Atlantic Croaker population dynamics during 1972–2008. In model 2, MWET was introduced into the intrinsic rate of population increase (r). For both models, a prior probability distribution (prior) was constructed for r or a scaling parameter (r0); imputs were the fishery removals, and fall biomass indices developed by using data from the Multispecies Bottom Trawl Survey of the Northeast Fisheries Science Center, National Marine Fisheries Service, and the Coastal Trawl Survey of the Southeast Area Monitoring and Assessment Program. Model sensitivity runs incorporated a uniform (0.01,1.5) prior for r or r0 and bycatch data from the shrimp-trawl fishery. All model variants produced similar results and therefore supported the conclusion of low risk of overfishing for the Atlantic Croaker stock in the 2000s. However, the data statistically supported only model 1 and its configuration that included the shrimp-trawl fishery bycatch. The process errors of these models showed slightly positive and significant correlations with MWET, indicating that warmer winters would enhance Atlantic Croaker biomass production. Inconclusive, somewhat conflicting results indicate that biomass dynamic models should not integrate MWET, pending, perhaps, accumulation of longer time series of the variables controlling the production dynamics of Atlantic Croaker, preferably including winter-induced estimates of Atlantic Croaker kills.

A 10-year time series of zooplankton anomalies off the British Columbia coast [abstract]

EXTRACT (SEE PDF FOR FULL ABSTRACT): Zooplankton biomass and species composition have been sampled since 1985 at a set of standard locations off Vancouver Island. From these data, I have estimated multi-year average seasonal cycles and time series of anomalies from these averages.

On the variation of the 2DEG charge density with the density of the surface donor traps in AiGaN/GaN transistors

Gallium nitride (GaN) has a bright future in high voltage device owing to its remarkable physical properties and the possibility of growing heterostructures on silicon substrates. GaN High Electron Mobility Transistors (HEMTs) are expected to make a strong impact in off line applications and LED drives. However, unlike in silicon-based power devices, the on-state resistance of HEMT devices is hugely influenced by donor and acceptor traps at interfaces and in the bulk. This study focuses on the influence of donor traps located at the top interface between the semiconductor layer and the silicon nitride on the 2DEG density. It is shown through TCAD simulations and analytical study that the 2DEG charge density has an 'S' shape variation with two distinctive 'flat' regions, wherein it is not affected by the donor concentration, and one linear region. wherein the channel density increases proportionally with the donor concentration. We also show that the upper threshold value of the donor concentration within this 'S' shape increases significantly with the AIGaN thickness and the Al mole fraction and is highly affected by the presence of a thin GaN cap layer. © 2013 IEEE.

Variational calculations of ionized-donor-bound excitons in GaAs-AlxGa1-xAs quantum wells

Using a two-parameter wave function, we calculate variationally the binding energy of an exciton bound to an ionized donor impurity (D+,X) in GaAs-AlxGa1-xAs quantum wells for the values of the well width from 10 to 300 Angstrom, when the dopant is located in the center of the well and at the edge of the well. The theoretical results confirm that the previous experimental speculation proposed by Reynolds tit al. [Phys. Rev. B 40, 6210 (1989)] is the binding energy of D+,X for the dopant at the edge of the well. in addition, we also calculate the center-of-mass wave function of the exciton and the average interparticle distances. The results are discussed in detail.

Binding energy of ionized-donor-bound excitons in the GaAs-AlxGa1-xAs quantum wells

The binding energy of an exciton bound to an ionized donor impurity (D+,X) located st the center or the edge in GaAs-AlxGa1-xAs quantum wells is calculated variationally for the well width from 10 to 300 Angstrom by using a two-parameter wave function, The theoretical results are discussed and compared with the previous experimental results.

EFFECTS OF AN EXTERNAL MAGNETIC-FIELD ON SHALLOW DONOR LEVELS IN SEMICONDUCTORS

An extension of Faulkner's method for the energy levels of the shallow donor in silicon and germanium at zero field is made in order to investigate the effects of a magnetic field upon the excited states. The effective-mass Hamiltonian matrix elements of an electron bound to a donor center and subjected to a magnetic field B, which involves both the linear and quadratic terms of magnetic field, are expressed analytically and matrices are solved numerically. The photothermal ionization spectroscopy of phosphorus in ultrapure silicon for magnetic fields parallel to the [1,0,0] and [1,1,1] directions and up to 10 T is explained successfully.

Entangled metal-organic frameworks modulated by N-donor ligands of different conformations

Based on the aromatic dicarboxylic acid and N-donor ligands with different conformations, four Zn(II) metal-organic frameworks, namely [Zn(mfda)(L-1)](1), [Zn-2(mfda)(2)(L-2)]center dot DMF center dot H2O (2), [Zn-2(mfda)(2)(L-3)(H2O)]center dot DMF (3) and [Zn-2(mfda)(2)(L-4)] (4) have been synthesized (mfda = 9,9-dimethylfluorene-2,7-dicarboxylate anion, L-1 = 1,10-phenanthroline, L-2 = 4,4 '-bipyridine, L-3 = 2,5-bis(4-pyridyl)-1,3,4-ocadiazole and L-4 = 1,4-bis(imidazol-1-ylmethyl)benzene). Single-crystal X-ray diffraction has revealed that all compounds exhibit entangled structures. Compound 1 is composed of 1D zigzag chains that are entangled through the pi-pi stacking interactions to generate a three-fold interpenetrating diamond-like networks.

Hydrothermal syntheses and crystal structures of bimetallic cluster complexes [{Cd(phen)(2)}(2)V4O12]center dot 5H(2)O and [Ni(phen)(3)](2)[V4O12]center dot 17.5H(2)O

The hydrothermal reactions of vanadium oxide starting materials with divalent transition metal cations in the presence of nitrogen donor chelating ligands yield the bimetallic cluster complexes with the formulae [{Cd(phen(2))(2)V4O12].5H(2)O (1) and [Ni(phen)(3)](2)[V4O12] . 17.5H(2)O (2). Crystal data: C48H52Cd2N8O22V4 (1), triclinic. P (1) over bar, a = 10.3366(10), b = 11.320(3), c = 13.268(3) Angstrom, alpha = 103.888(17)degrees, beta = 92.256(15)degrees, gamma = 107.444(14)degrees, Z = 1; C72H131N12Ni2O29.5V4 (2), triclinic. P (1) over bar, a = 12.305(3), b = 13.172(6), c = 15.133(4), alpha = 79.05(3)degrees, beta = 76.09(2)degrees, gamma = 74.66(3)degrees, Z = 1. Data were collected on a Siemens P4 four-circle diffractometer at 293 K in the range 1.59degrees < theta < 26.02degrees and 2.01degrees < 0 < 25.01degrees using the omega-scan technique, respectively. The structure of 1 consists of a [V4O12](4-) cluster covalently attached to two {Cd(phen)(2)}(2+) fragments, in which the [V4O12](4-) cluster adopts a chair-like configuration. In the structure of 2, the [V4O12](4-) cluster is isolated. And the complex formed a layer structure via hydrogen bonds between the V4O12](4-) unit and crystallization water molecules.

Hydrothermal synthesis and characterization of bimetallic cluster complex [{Mn(phen)(2)}(2)V4O12]center dot 1/2 H2O

A new bimetallic cluster complex with the formula [(Mn(phen)(2))(2)V4O12].1/2 H2O has been synthesized through hydrothermal reaction of vanadate staring material with manganese cation in the presence of nitrogen donor chelating ligand and characterized by single-crystal X-ray diffraction, elemental analysis, IR UV-vis, ESR spectrum and thermal analysis. The compound crystallize in the monoclinic space group P2(1)/c with a = 18.475(4) Angstrom, b = 11.473(2) Angstrom, c = 23.667(5) Angstrom, beta = 97.76(3)degrees, V = 4971(2) Angstrom(3) and Z = 4. The structure of [{Mn(phen)(2)}(2)V4O12].1/2 H2O is composed of a discrete V4O124- cluster covalently attached to two [Mn(phen)(2)](2+) fragments.

When the library is located in prime real estate: a case study on the loss of space from the Duke University Medical Center Library and Archives.

The Duke University Medical Center Library and Archives is located in the heart of the Duke Medicine campus, surrounded by Duke Hospital, ambulatory clinics, and numerous research facilities. Its location is considered prime real estate, given its adjacency to patient care, research, and educational activities. In 2005, the Duke University Library Space Planning Committee had recommended creating a learning center in the library that would support a variety of educational activities. However, the health system needed to convert the library's top floor into office space to make way for expansion of the hospital and cancer center. The library had only five months to plan the storage and consolidation of its journal and book collections, while working with the facilities design office and architect on the replacement of key user spaces on the top floor. Library staff worked together to develop plans for storing, weeding, and consolidating the collections and provided input into renovation plans for users spaces on its mezzanine level. The library lost 15,238 square feet (29%) of its net assignable square footage and a total of 16,897 (30%) gross square feet. This included 50% of the total space allotted to collections and over 15% of user spaces. The top-floor space now houses offices for Duke Medicine oncology faculty and staff. By storing a large portion of its collection off-site, the library was able to remove more stacks on the remaining stack level and convert them to user spaces, a long-term goal for the library. Additional space on the mezzanine level had to be converted to replace lost study and conference room spaces. While this project did not match the recommended space plans for the library, it underscored the need for the library to think creatively about the future of its facility and to work toward a more cohesive master plan.

Costimulation blockade alters germinal center responses and prevents antibody-mediated rejection.

De novo donor-specific antibody (DSA) after organ transplantation promotes antibody-mediated rejection (AMR) and causes late graft loss. Previously, we demonstrated that depletion using anti-CD3 immunotoxin combined with tacrolimus and alefacept (AMR regimen) reliably induced early DSA production with AMR in a nonhuman primate kidney transplant model. Five animals were assigned as positive AMR controls, four received additional belatacept and four received additional anti-CD40 mAb (2C10R4). Notably, production of early de novo DSA was completely attenuated with additional belatacept or 2C10R4 treatment. In accordance with this, while positive controls experienced a decrease in peripheral IgM(+) B cells, bela- and 2C10R4-added groups maintained a predominant population of IgM(+) B cells, potentially indicating decreased isotype switching. Central memory T cells (CD4(+) CD28(+) CD95(+)) as well as PD-1(hi) CD4(+) T cells were decreased in both bela-added and 2C10R4-added groups. In analyzing germinal center (GC) reactions in situ, lymph nodes further revealed a reduction of B cell clonal expansion, GC-follicular helper T (Tfh) cells, and IL-21 production inside GCs with additional belatacept or 2C10R4 treatment. Here we provide evidence that belatacept and 2C10R4 selectively suppresses the humoral response via regulating Tfh cells and prevents AMR in this nonhuman primate model.

Electronic structure of the nitrogen-vacancy center in diamond from first-principles theory

The nitrogen-vacancy (NV) center is a paramagnetic defect in diamond with applications as a qubit. Here, we investigate its electronic structure by using ab initio density functional theory for five different NV center models of two different cluster sizes. We describe the symmetry and energetics of the low-lying states and compare the optical frequencies obtained to experimental results. We compute the major transition of the negatively charged NV centers to within 25–100 meV accuracy and find that it is energetically favorable for substitutional nitrogens to donate an electron to NV0. The excited state of the major transition and the NV0 state with a neutral donor nitrogen are found to be close in energy.

Business development in Siemens global shared services delivery center Portugal

A Work Project, presented as part of the requirements for the Award of a Masters Degree in Management from the NOVA – School of Business and Economics