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.

Origin of Th/U variations in chondritic meteorites

Isotope dilution thorium and uranium analyses of the Harleton chondrite show a larger scatter than previously observed in equilibrated ordinary chondrites (EOC). The linear correlation of Th/U with 1/U in Harleton (and all EOC data) is produced by variation in the chlorapatite to merrillite mixing ratio. Apatite variations control the U concentrations. Phosphorus variations are compensated by inverse variations in U to preserve the Th/U vs. 1/U correlation. Because the Th/U variations reflect phosphate ampling, a weighted Th/U average should converge to an improved solar system Th/U. We obtain Th/U=3.53 (1_-mean=0.10), significantly lower and more precise than previous estimates.

To test whether apatite also produces Th/U variation in CI and CM chondrites, we performed P analyses on the solutions from leaching experiments of Orgueil and Murchison meteorites.

A linear Th/U vs. 1/U correlation in CI can be explained by redistribution of hexavalent U by aqueous fluids into carbonates and sulfates.

Unlike CI and EOC, whole rock Th/U variations in CMs are mostly due to Th variations. A Th/U vs. 1/U linear correlation suggested by previous data for CMs is not real. We distinguish 4 components responsible for the whole rock Th/U variations: (1) P and actinide-depleted matrix containing small amounts of U-rich carbonate/sulfate phases (similar to CIs); (2) CAIs and (3) chondrules are major reservoirs for actinides, (4) an easily leachable phase of high Th/U. likely carbonate produced by CAI alteration. Phosphates play a minor role as actinide and P carrier phases in CM chondrites.

Using our Th/U and minimum galactic ages from halo globular clusters, we calculate relative supernovae production rates for ²³²Th/²³⁸U and ²³⁵U/²³⁸U for different models of r-process nucleosynthesis. For uniform galactic production, the beginning of the r-process nucleosynthesis must be less than 13 Gyr. Exponentially decreasing production is also consistent with a 13 Gyr age, but very slow decay times are required (less than 35 Gyr), approaching the uniform production. The 15 Gyr Galaxy requires either a fast initial production growth (infall time constant less than 0.5 Gyr) followed by very low decrease (decay time constant greater than 100 Gyr), or the fastest possible decrease (≈8 Gyr) preceded by slow in fall (≈7.5 Gyr).

Hunting spectro-temporal information in unevenly spaced paleoclimate time series

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Evolução geológica do Complexo Quirino, Terreno Paraíba do Sul, Setor Central da Faixa Ribeira, com base em dados isotópicos de Sm-Nd e Sr

A área estudada está inserida na Faixa Ribeira, Segmento Central da Província Mantiqueira (Almeida et al., 1973, 1977, 1981), que representa um cinturão de dobramentos e empurrões gerado no Neo-proterozóico/Cambriano, durante a Orogênese Brasiliana, na borda sul/sudeste do Cráton do São Francisco (Almeida, 1971, 1977; Cordani et al., 1967, 1973; Cordani & Brito Neves, 1982; Teixeira & Figueiredo, 1991). Neste contexto, o Complexo Quirino é o embasamento retrabalhado do Terreno Paraíba do Sul (Heilbron et al., 2004). O Complexo Quirino é formado por extensos corpos de ortognaisses foliados a homogêneos, leuco a mesocráticos, de granulometria média à grossa, composicionalmente variando entre granitóides tonalíticos/granodioríticos a graníticos, e apresentando enclaves de rochas ultramáficas, máficas e cálcio-silicáticas (ricas em tremolita). Os ortognaisses tonalíticos/granodioríticos apresentam porfiroblastos de plagioclásio e a hornblenda como máfico principal, contrastando com os de composição granítica que apresentam porfiroblastos de K-feldspato e biotita predominante. Como acessórios aparecem zircão, titanita, apatita e epidoto. Também estão associados a estes ortognaisses, granitóides neoproterozóicos que formam corpos individualizados ou lentes anatéticas no conjunto paleoproterozóico. Estes são compostos predominantemente por biotita gnaisse e hornblenda-biotita gnaisse. A análise litogeoquímicas dos ortognaisses do Complexo Quirino demonstrou a existência de duas séries magmáticas distintas. A primeira pertencente à série cálcio-alcalina de alto-K apresenta uma composição mais expandida granítica-adamelítica/granodioritica/tonalítica e é correlacionável aos bt-ortognaisses e alguns hb-bt-ortognaisses. Os ortognaisses da série médio-K apresentam composição predominantemente tonalítica, sendo correlacionáveis à maioria dos hornblenda-biotita gnaisses. Enclaves lenticulares de metapiroxeníticos e anfibolíticos ocorrem em muitos afloramentos. Também ocorrem granitóides neoproterozóicos de composição graníticas a quartzo-monzoníticas O estudo isotópico de Sm-Nd e Sr demonstrou que os ortognaisses da série cálcio-alcalina de alto-K e aqueles da série cálcio-alcalina de médio-K possuem idades modelo TDM variando entre paleoproterozóicas a arqueanas, consistentes com dados U-Pb em zircão publicados na literatura. A série cálcio-alcalina de alto-K é mais antiga (2308 9,2 Ma a 2185 8 Ma) do que a série calcio-alcalina de médio-K (2169 3 a 2136 14 Ma) e a existência de zircões herdados com idades mínimas de 2846 Ma e 2981 Ma para série de médio-K e 3388 16 para série de alto-K. Os granitóides brasilianos possuem idades de cristalização neoproterozóica correlacionada a Orogênese Brasiliana (602 a 627 Ma) (Viana, 2008; Valladares et al., 2002)./Com base nos dados de Sr e Sm-Nd foi possível caracterizar 4 grupos distintos. Os grupos 1 e 2 são formados por rochas de idade paleoproterozóica (2,1 a 2,3 Ga) com idades modelo TDM variando de 2,9 e 3,4 Ga, εNd entre -8,1 e -5,8 e 87Sr/86Sr(t) = 0,694707 (Grupo 1) e TDM variando de 2,5 a 2,7 Ga, εNd entre -5,8 e -3,1 e 87Sr/86Sr(t) = 0,680824 (Grupo 2), formados no paleoproterozóico com contribuição de uma crosta arqueana. O grupo 3 é formado por rochas juvenis de idade paleoproterozóica, com idades de cristalização variando entre 2,0 e 2,2 Ga e com idades modelo TDM variando de 2,1 a 2,2 Ga e εNd entre + 1,5 e + 1,2. O grupo 4 é formado durante o neoproterozóico (645 Ma) por rochas possivelmente de idade paleoproterozóico com idades modelo TDM igual a 1,7 Ga e εNd igual a -8,3.

基于U形塑料光纤的氧气传感器

报道了一种基于荧光猝灭原理的光纤氧气传感器.采用塑料光纤作为传感和传光元件进行氧气传感,传感头制成U形.以邻菲咯啉钌作为荧光标记物,用溶胶-凝胶法制备敏感材料.采用相移法来实现对荧光寿命的测定.测量了不同弯曲半径传感头对氧气传感的灵敏度,发现当U形光纤的弯曲半径较小时系统的灵敏度较高.对荧光寿命和氧气浓度的关系进行了测量,发现二者呈亚线性关系,提出双荧光体模型解释这一实验现象.

基于U型塑料光纤和邻啡咯啉钌的溶解氧传感器

本文提出了一种基于U型塑料光纤和邻啡咯啉钌的溶解氧传感器。光纤传感头放在样品池中，测量了不同氮氧体积比情况下荧光强度和寿命。研究了邻啡咯啉钌的浓度、传感头的退火时间和U型光纤的弯曲半径对系统灵敏度的影响。我们提出了双层模型来解释实验结果不符合S-V方程的实验现象，并用双层模型分析了弯曲半径对系统灵敏度的影响。通过对溶解氧浓度和荧光寿命亚线性曲线的拟合，我们得出敏感层的厚度和S-V系数分别为0.59和0.61。

The possibilities and dangers in using malachite green in pisciculture.[Translation from: Informatsionnyi Byulleten Biologiya Vnutrennikh Vod No.3 17-21, 1969.]

For many years a dye has been used in the practise of pisciculture and pond management, which is known by the name of malachite green, and is used to combat fungus on fish, fish eggs and external animal parasites on fish. The authors describe the problem of the application of malachite green in pisciculture and undertake special, complementary research.

Investigations on the vertical migration of planktonic Crustacea in the Bodensee-Obersee. [Translation from: Schriften des Vereins fur Geschichte des Bodensees und seiner Umgebung, 87, 177-187, 1969.]

The vertical zoning of the planktonic Crustacea in a lake is the expression of a complex set of different factors. Besides the measurable, external influences such as light, temperature, acid and C02 stratification, a particularly large part is played by internal factors, which co-ordinate a specific reaction in each species depending on state of development, age and sex. Supporting this extensive, predictable, annual course of diurnal depths and the daily vertical migrations, whose extent is again dependent on external conditions, primarily of course on the amount of light. The individual factors mentioned, however, are here also of great significance. Within the scope of a long-term study of the planktonic Copepoda of Lake Constance, some day and night series were in 1963 also carried out in the Obersee, in order to obtain at least volumetric data on the extent of the daily migrations of these creatures.