The organometallic chemistry of the Ru(001) surface

The organometallic chemistry of the hexagonally close-packed Ru(001) surface has been studied using electron energy loss spectroscopy and thermal desorption mass spectrometry. The molecules that have been studied are acetylene, formamide and ammonia. The chemistry of acetylene and formamide has also been investigated in the presence of coadsorbed hydrogen and oxygen adatoms.

Acetylene is adsorbed molecularly on Ru(001) below approximately 230 K, with rehybridization of the molecule to nearly sp^3 occurring. The principal decomposition products at higher temperatures are ethylidyne (CCH_3) and acetylide (CCH) between 230 and 350 K, and methylidyne (CH) and surface carbon at higher temperatures. Some methylidyne is stable to approximately 700 K. The preadsorption of hydrogen does not alter the decomposition products of acetylene, but reduces the saturation coverage and also leads to the formation of a small amount of ethylene (via an η^2-CHCH_2 species) which desorbs molecularly near 175 K. Preadsorbed oxygen also reduces the saturation coverage of acetylene but has virtually no effect on the nature of the molecularly chemisorbed acetylene. It does, however, lead to the formation of an sp^2-hybridized vinylidene (CCH_2) species in the decomposition of acetylene, in addition to the decomposition products that are formed on the clean surface. There is no molecular desorption of chemisorbed acetylene from clean Ru(001), hydrogen-presaturated Ru(001), or oxygen-presaturated Ru(001).

The adsorption and decomposition of formamide has been studied on clean Ru(001), hydrogen-presaturated Ru(001), and Ru(001)-p(1x2)-O (oxygen adatom coverage = 0.5). On clean Ru(001), the adsorption of low coverages of formamide at 80 K results in CH bond cleavage and rehybridization of the carbonyl double bond to produce an η^2 (C,O)-NH_2CO species. This species is stable to approximately 250 K at which point it decomposes to yield a mixture of coadsorbed carbon monoxide, ammonia, an NH species and hydrogen adatoms. The decomposition of NH to hydrogen and nitrogen adatoms occurs between 350 and 400 K, and the thermal desorption products are NH_3 (-315 K), H_2 (-420 K), CO (-480 K) and N_2 (-770 K). At higher formamide coverages, some formamide is adsorbed molecularly at 80 K, leading both to molecular desorption and to the formation of a new surface intermediate between 300 and 375 K that is identified tentatively as η^1(N)-NCHO. On Ru(001)- p(1x2)-O and hydrogen-presaturated Ru(001), formamide adsorbs molecularly at 80 K in an η^1(O)- NH_2CHO configuration. On the oxygen-precovered surface, the molecularly adsorbed formamide undergoes competing desorption and decomposition, resulting in the formation of an η^2(N,O)-NHCHO species (analogous to a bidentate formate) at approximately 265 K. This species decomposes near 420 K with the evolution of CO and H_2 into the gas phase. On the hydrogen precovered surface, the Η^1(O)-NH_2CHO converts below 200 K to η^2(C,O)-NH_2CHO and η^2(C,O)-NH^2CO, with some molecular desorption occurring also at high coverage. The η^2(C,O)-bonded species decompose in a manner similar to the decomposition of η^2(C,O)-NH_2CO on the clean surface, although the formation of ammonia is not detected.

Ammonia adsorbs reversibly on Ru(001) at 80 K, with negligible dissociation occurring as the surface is annealed The EEL spectra of ammonia on Ru(001) are very similar to those of ammonia on other metal surfaces. Off-specular EEL spectra of chemisorbed ammonia allow the v(Ru-NH_3) and ρ(NH_3) vibrational loss features to be resolved near 340 and 625 cm^(-1), respectively. The intense δ_g (NH_3) loss feature shifts downward in frequency with increasing ammonia coverage, from approximately 1160 cm^(-1) in the low coverage limit to 1070 cm^(-1) at saturation. In coordination compounds of ammonia, the frequency of this mode shifts downward with decreasing charge on the metal atom, and its downshift on Ru(001) can be correlated with the large work function decrease that the surface has previously been shown to undergo when ammonia is adsorbed. The EELS data are consistent with ammonia adsorption in on-top sites. Second-layer and multilayer ammonia on Ru(001) have also been characterized vibrationally, and the results are similar to those obtained for other metal surfaces.

The effect of long term exploitation by the gill net fishery on the multispecies fish stocks in Kainji Lake, Nigeria, 1969-1997

The findings are presented of an assessment made of the gillnet fishery in Kainji Lake, Nigeria from 1969 to the present, on the basis of data sets from commercial and experimental gillnet fishing, with the purpose to detect trends in some key fishery monitoring indicators. During this period, there has been an increase in the number of small meshed nets in the fishery resulting in a shift in the mode to lower mesh sizes; consequently, the average mesh size declined gradually in the fishery. This trend is found to be directly correlated with the decline in the CPUE and mean weight of the fish species. It is argued that the observed trend in CPUE and mean weight is forcing the fishermen to switch effort to gears such as traps which have very small meshes and can indescriminately take all sizes of the fish. It is shown that the catch composition by weight of Citharinus citharus, Lates niloticus and tilapias declined in the gillnet fishery in the late 70's and early 80's. Recent data, from 1994 to 1996, however indicates that C. citharus is recovering, but with declining mean weight. This suggests that the exploitation pattern is shifting to the smaller fish through the use of small meshed nets. In general, however, there has not been drastic changes in species bio-diversity in the Lake as a result of predatory effect and ecosystem overfishing as has happened in other great African Lakes. The species composition since lake formation continued to be dominated by fewer that 20 species. The potential yield for the lake has been estimated to be 32,166 tonnes (excluding clupeids) and the required optimum fishing effort to be 1,814 fishing canoes. In view of the relative stability of the species diversity in the lake and the current fish production level, it is proposed here that this MSY be adopted for all species. This would be achieved with the current effort level in the lake assuming that the efficiency of the fishermen and their gears do not improve. It should be reviewed after 10 or more years of catch and effort data collection. (PDF contains 65 pages)

Report of the Inter-American Tropical Tuna Commission for the year 1969

ENGLISH: The Inter-American Tropical Tuna Commission operates under the authority and direction of a convention originally entered into by the Republic of Costa Rica and the United States of America. The convention, which came into force in 1950, is open to adherence by other governments whose nationals fish for tropical tunas in the eastern Pacific Ocean. Under this provision the Republic of Panama adhered in 1953, the Republic of Ecuador in 1961, the United Mexican States in 1964 and Canada in 1968. In 1967, Ecuador gave notice of her intent to withdraw from the Commission, and her withdrawal became effective on August 21, 1968. SPANISH: La Comisión Interamericana del Atún Tropical está bajo la autoridad y dirección de una convención la cual fue originalmente formada por la República de Costa Rica y los Estados Unidos de América. La Convención, vigente desde 1950, está abierta a la afiliación de otros gobiernos cuyos nacionales pesquen túnidos en el Pacifico oriental tropical. Bajo esta medida la República de Panamá se afilió en 1953, la República del Ecuador en 1961, los Estados Unidos Mexicanos en 1964, y Canadá en 1968. En 1967, el Ecuador anunció su intención de retirarse de la Comisión y la renuncia se hizo efectiva el 21 de agosto de 1968. (PDF contains 117 pages.)

Structure, chemistry, and energetics of organic and inorganic adsorbates on Ga-rich GaAs and GaP(001) surfaces

The work described in this dissertation includes fundamental investigations into three surface processes, namely inorganic film growth, water-induced oxidation, and organic functionalization/passivation, on the GaP and GaAs(001) surfaces. The techniques used to carry out this work include scanning tunneling microscopy (STM), X-ray photoelectron spectroscopy (XPS), and density functional theory (DFT) calculations. Atomic structure, electronic structure, reaction mechanisms, and energetics related to these surface processes are discussed at atomic or molecular levels.

First, we investigate epitaxial Zn₃P₂ films grown on the Ga-rich GaAs(001)(6×6) surface. The film growth mechanism, electronic properties, and atomic structure of the Zn₃P₂/GaAs(001) system are discussed based on experimental and theoretical observations. We discover that a P-rich amorphous layer covers the crystalline Zn3P2 film during and after growth. We also propose more accurate picture of the GaP interfacial layer between Zn₃P₂ and GaAs, based on the atomic structure, chemical bonding, band diagram, and P-replacement energetics, than was previously anticipated.

Second, DFT calculations are carried out in order to understand water-induced oxidation mechanisms on the Ga-rich GaP(001)(2×4) surface. Structural and energetic information of every step in the gaseous water-induced GaP oxidation reactions are elucidated at the atomic level in great detail. We explore all reasonable ground states involved in most of the possible adsorption and decomposition pathways. We also investigate structures and energies of the transition states in the first hydrogen dissociation of a water molecule on the (2×4) surface.

Finally, adsorption structures and thermal decomposition reactions of 1-propanethiol on the Ga-rich GaP(001)(2×4) surface are investigated using high resolution STM, XPS, and DFT simulations. We elucidate adsorption locations and their associated atomic structures of a single 1-propanethiol molecule on the (2×4) surface as a function of annealing temperature. DFT calculations are carried out to optimize ground state structures and search transition states. XPS is used to investigate variations of the chemical bonding nature and coverage of the adsorbate species.

Studies of molecular bonding, interactions and decomposition reactions on the (001) surface of ruthenium

The interactions of N₂, formic acid and acetone on the Ru(001) surface are studied using thermal desorption mass spectrometry (TDMS), electron energy loss spectroscopy (EELS), and computer modeling.

Low energy electron diffraction (LEED), EELS and TDMS were used to study chemisorption of N₂ on Ru(001). Adsorption at 75 K produces two desorption states. Adsorption at 95 K fills only the higher energy desorption state and produces a (√3 x √3)R30° LEED pattern. EEL spectra indicate both desorption states are populated by N₂ molecules bonded "on-top" of Ru atoms.

Monte Carlo simulation results are presented on Ru(001) using a kinetic lattice gas model with precursor mediated adsorption, desorption and migration. The model gives good agreement with experimental data. The island growth rate was computed using the same model and is well fit by R(t)^m - R(t₀)^m = At, with m approximately 8. The island size was determined from the width of the superlattice diffraction feature.

The techniques, algorithms and computer programs used for simulations are documented. Coordinate schemes for indexing sites on a 2-D hexagonal lattice, programs for simulation of adsorption and desorption, techniques for analysis of ordering, and computer graphics routines are discussed.

The adsorption of formic acid on Ru(001) has been studied by EELS and TDMS. Large exposures produce a molecular multilayer species. A monodentate formate, bidentate formate, and a hydroxyl species are stable intermediates in formic acid decomposition. The monodentate formate species is converted to the bidentate species by heating. Formic acid decomposition products are CO₂, CO, H₂, H₂O and oxygen adatoms. The ratio of desorbed CO with respect to CO₂ increases both with slower heating rates and with lower coverages.

The existence of two different forms of adsorbed acetone, side-on, bonded through the oxygen and acyl carbon, and end-on, bonded through the oxygen, have been verified by EELS. On Pt(111), only the end-on species is observed. On dean Ru(001) and p(2 x 2)O precovered Ru(001), both forms coexist. The side-on species is dominant on clean Ru(001), while O stabilizes the end-on form. The end-on form desorbs molecularly. Bonding geometry stability is explained by surface Lewis acidity and by comparison to organometallic coordination complexes.

Cartas enviadas por Modesto Bargalló a Justo Garate entre 1967 y 1969

5 cartas (mecanografiadas) ; 215x140mm

Kinetic investigations of heterogeneously catalyzed reactions on the Ru(001) and Pt(110)-(1x2) surfaces

The initial probabilities of activated, dissociative chemisorption of methane and ethane on Pt(110)-(1 x 2) have been measured. The surface temperature was varied from 450 to 900 K with the reactant gas temperature constant at 300 K. Under these conditions, we probe the kinetics of dissociation via trapping-mediated (as opposed to 'direct') mechanism. It was found that the probabilities of dissociation of both methane and ethane were strong functions of the surface temperature with an apparent activation energies of 14.4 kcal/mol for methane and 2.8 kcal/mol for ethane, which implys that the methane and ethane molecules have fully accommodated to the surface temperature. Kinetic isotope effects were observed for both reactions, indicating that the C-H bond cleavage was involved in the rate-limiting step. A mechanistic model based on the trapping-mediated mechanism is used to explain the observed kinetic behavior. The activation energies for C-H bond dissociation of the thermally accommodated methane and ethane on the surface extracted from the model are 18.4 and 10.3 kcal/mol, respectively.

The studies of the catalytic decomposition of formic acid on the Ru(001) surface with thermal desorption mass spectrometry following the adsorption of DCOOH and HCOOH on the surface at 130 and 310 K are described. Formic acid (DCOOH) chemisorbs dissociatively on the surface via both the cleavage of its O-H bond to form a formate and a hydrogen adatom, and the cleavage of its C-O bond to form a carbon monoxide, a deuterium adatom and an hydroxyl (OH). The former is the predominant reaction. The rate of desorption of carbon dioxide is a direct measure of the kinetics of decomposition of the surface formate. It is characterized by a kinetic isotope effect, an increasingly narrow FWHM, and an upward shift in peak temperature with Ɵ_T, the coverage of the dissociatively adsorbed formic acid. The FWHM and the peak temperature change from 18 K and 326 K at Ɵ_T = 0.04 to 8 K and 395 K at Ɵ_T = 0.89. The increase in the apparent activation energy of the C-D bond cleavage is largely a result of self-poisoning by the formate, the presence of which on the surface alters the electronic properties of the surface such that the activation energy of the decomposition of formate is increased. The variation of the activation energy for carbon dioxide formation with Ɵ_T accounts for the observed sharp carbon dioxide peak. The coverage of surface formate can be adjusted over a relatively wide range so that the activation energy for C-D bond cleavage in the case of DCOOH can be adjusted to be below, approximately equal to, or well above the activation energy for the recombinative desorption of the deuterium adatoms. Accordingly, the desorption of deuterium was observed to be governed completely by the desorption kinetics of the deuterium adatoms at low Ɵ_T, jointly by the kinetics of deuterium desorption and C-D bond cleavage at intermediate Ɵ_T, and solely by the kinetics of C-D bond cleavage at high Ɵ_T. The overall branching ratio of the formate to carbon dioxide and carbon monoxide is approximately unity, regardless the initial coverage Ɵ_T, even though the activation energy for the production of carbon dioxide varies with Ɵ_T. The desorption of water, which implies C-O bond cleavage of the formate, appears at approximately the same temperature as that of carbon dioxide. These observations suggest that the cleavage of the C-D bond and that of the C-O bond of two surface formates are coupled, possibly via the formation of a short-lived surface complex that is the precursor to to the decomposition.

The measurement of steady-state rate is demonstrated here to be valuable in determining kinetics associated with short-lived, molecularly adsorbed precursor to further reactions on the surface, by determining the kinetic parameters of the molecular precursor of formaldehyde to its dissociation on the Pt(110)-(1 x 2) surface.

Overlayers of nitrogen adatoms on Ru(001) have been characterized both by thermal desorption mass spectrometry and low-energy electron diffraction, as well as chemically via the postadsorption and desorption of ammonia and carbon monoxide.

The nitrogen-adatom overlayer was prepared by decomposing ammonia thermally on the surface at a pressure of 2.8 x 10^(-6) Torr and a temperature of 480 K. The saturated overlayer prepared under these conditions has associated with it a (√247/10 x √247/10)R22.7° LEED pattern, has two peaks in its thermal desorption spectrum, and has a fractional surface coverage of 0.40. Annealing the overlayer to approximately 535 K results in a rather sharp (√3 x √3)R30° LEED pattern with an associated fractional surface coverage of one-third. Annealing the overlayer further to 620 K results in the disappearance of the low-temperature thermal desorption peak and the appearance of a rather fuzzy p(2x2) LEED pattern with an associated fractional surface coverage of approximately one-fourth. In the low coverage limit, the presence of the (√3 x √3)R30° N overlayer alters the surface in such a way that the binding energy of ammonia is increased by 20% relative to the clean surface, whereas that of carbon monoxide is reduced by 15%.

A general methodology for the indirect relative determination of the absolute fractional surface coverages has been developed and was utilized to determine the saturation fractional coverage of hydrogen on Ru(001). Formaldehyde was employed as a bridge to lead us from the known reference point of the saturation fractional coverage of carbon monoxide to unknown reference point of the fractional coverage of hydrogen on Ru(001), which is then used to determine accurately the saturation fractional coverage of hydrogen. We find that ƟSAT/H = 1.02 (±0.05), i.e., the surface stoichiometry is Ru : H = 1 : 1. The relative nature of the method, which cancels systematic errors, together with the utilization of a glass envelope around the mass spectrometer, which reduces spurious contributions in the thermal desorption spectra, results in high accuracy in the determination of absolute fractional coverages.

Life cycle of Pisidium obtusale Jenyns. [Translation from: Informatsionnyi Byulleten Biologiya Vnutrennikh Vod No.3 17-21, 1969.]

Pisidium obtusale in the neighbourhood of Borka occurs in deep pools on upland bogs. The majority of water-bodies where this mollusc lives are temporary. Their bottoms are covered with sedges, and sometimes mosses occur. Evidently there is a marked attraction of P. obtusale to places overgrown by willow. In pools remote from scrub or woody vegetation it does not appear. Temporary water-bodies fill up with melt water in the middle or the end of April and finally dry up at the end of July or the beginning of August. Observations on the life cycle of P. obtusale started on 21 April 1966, following on the filling-up of the water-body by melt water. The findings of the study are presented in this paper.

Tests of some specific effect substances in duck nutrition. Translation from: Biologisace a chemisaze vyzivy svirat 5, 43-48, 1969.]

There is a constantly increasing collection of manufactured substances, whose effectiveness in the sustenance of ducks is under investigation. The author examines the effects of some substances already previously tested and also there were examined substances which had not hitherto been studied. The use of different supplements for late autumn fattening is studied through various experiments.

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.

Rhythms of division of some algae in situ and in laboratory culture. [Translation from: Studii Cerc.Biol.(Bot.) 21, 61-65, 1969. ]

The rhythm of division of 9 species belonging to different groups of algae were analysed in situ and in the laboratory. The research which developed in different environmental conditions attempted to establish the capacity for multiplication and assimilation of chlorophyll on the part of the algae under study with a view to placing them in a culture. The results obtained showed that the green multicellular algae (eg. Ulothrix) and the blue algae (eg. Lyngbya, Oscillatoria) are able to produce an appreciable quantity of dry matter, just as the unicellular algae. At the same time it arises that amongst the numerous factors of the environment, temperature plays one of the most important roles in the process of multiplication.

Significance of the photoperiod for the development of Cyclops vicinus. [Translation from: Zoologischer Anzeiger Supplementband 33, 190-195, 1969.]

The significance of the photoperiod, a well-known phenomenon with arthropods, for the development of Cyclops vicinus were studied in laboratory conditions. There are indications that the point of the development process (development of the eggs and proportion of sexes) can be influenced through the photoperiod.

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.

Growth and reproduction of Moina rectirostris (Leydig) and Ceriodaphnia quadrangula (O. F. Muller) with feeding on detritus. [Translation from: Sbornik po prudovomu rybovodstvu, 79-89. Moscow, VNIRO, 1969.]

The significance of detritus in the nutrition of aquatic animals, especially of the small representatives of the zooplankton, has been studied very slightly. Research so far has established that in M. rectirostris with feeding on protococcal and single-celled green algae and bacteria the beginning of formation of eggs takes place in 2 - 4 days. The young appear in 4 - 6 days. In this study M. rectirostris and C. quadrangula are fed on detritus of natural origin in laboratory conditions. In order to determine the assimilability and productive: effect of detritus, the author set up experiments, permitting to characterize the rate of growth, speed of maturing and fertility of M. rectirostris and C. quadrangula with feeding of them on detritus of different composition and age.

'Fa Tsai', a Chinese edible Nostoc in market. [Translation from: Bulletin of the Japanese Society of Phycology 8 124-126, 1960. ]

The Nostoc 'Fa Tsai' is sometimes seen in Chinese cooking materials stores. It is investigated what 'Fa Tsai' consists of and where it originates.