Deposits of clastic carbonate-dominated (calciclastic) sedimentary slope systems in the rock record have been identified mostly as linearly-consistent carbonate apron deposits, even though most ancient clastic carbonate slope deposits fit the submarine fan systems better. Calciclastic submarine fans are consequently rarely described and are poorly understood. Subsequently, very little is known especially in mud-dominated calciclastic submarine fan systems. Presented in this study are a sedimentological core and petrographic characterisation of samples from eleven boreholes from the Lower Carboniferous of Bowland Basin (Northwest England) that reveals a >250 m thick calciturbidite complex deposited in a calciclastic submarine fan setting. Seven facies are recognised from core and thin section characterisation and are grouped into three carbonate turbidite sequences. They include: 1) Calciturbidites, comprising mostly of highto low-density, wavy-laminated bioclast-rich facies; 2) low-density densite mudstones which are characterised by planar laminated and unlaminated muddominated facies; and 3) Calcidebrites which are muddy or hyper-concentrated debrisflow deposits occurring as poorly-sorted, chaotic, mud-supported floatstones. These

Phd by thesis

Platinum-based heterogeneous catalysts are critical to many important commercial chemical processes, but their efficiency is extremely low on a per metal atom basis, because only the surface active-site atoms are used. Catalysts with single-atom dispersions are thus highly desirable to maximize atom efficiency, but making them is challenging. Here we report the synthesis of a single-atom catalyst that consists of only isolated single Pt atoms anchored to the surfaces of iron oxide nanocrystallites. This single-atom catalyst has extremely high atom efficiency and shows excellent stability and high activity for both CO oxidation and preferential oxidation of CO in H-2. Density functional theory calculations show that the high catalytic activity correlates with the partially vacant 5d orbitals of the positively charged, high-valent Pt atoms, which help to reduce both the CO adsorption energy and the activation barriers for CO oxidation.

Single-atom catalysis of CO oxidation using Pt1/FeOx

"Chemists familiar with conventional quantum mechanics will applaud and benefit greatly from this particularly instructive, thorough and clearly written exposition of density functional theory: its basis, concepts, terms, implementation, and performance in diverse applications. Users of DFT for structure, energy, and molecular property computations, as well as reaction mechanism studies, are guided to the optimum choices of the most effective methods. Well done!" Paul von RaguE Schleyer "A conspicuous hole in the computational chemist's library is nicely filled by this book, which provides a wide-ranging and pragmatic view of the subject.[...It] should justifiably become the favorite text on the subject for practioneers who aim to use DFT to solve chemical problems." J. F. Stanton, J. Am. Chem. Soc. "The authors' aim is to guide the chemist through basic theoretical and related technical aspects of DFT at an easy-to-understand theoretical level. They succeed admirably." P. C. H. Mitchell, Appl. Organomet. Chem. "The authors have done an excellent service to the chemical community. [...] A Chemist's Guide to Density Functional Theory is exactly what the title suggests. It should be an invaluable source of insight and knowledge for many chemists using DFT approaches to solve chemical problems." M. Kaupp, Angew. Chem.

A Chemist's Guide to Density Functional Theory

Fenton chemistry encompasses reactions of hydrogen peroxide in the presence of iron to generate highly reactive species such as the hydroxyl radical and possibly others. In this review, the complex mechanisms of Fenton and Fenton-like reactions and the important factors influencing these reactions, from both a fundamental and practical perspective, in applications to water and soil treatment, are discussed. The review covers modified versions including the photoassisted Fenton reaction, use of chelated iron, electro-Fenton reactions, and Fenton reactions using heterogeneous catalysts. Sections are devoted to nonclassical pathways, by-products, kinetics and process modeling, experimental design methodology, soil and aquifer treatment, use of Fenton in combination with other advanced oxidation processes or biodegradation, economic comparison with other advanced oxidation processes, and case studies.

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Advanced Oxidation Processes for Organic Contaminant Destruction Based on the Fenton Reaction and Related Chemistry

The Cationminus signpi Interaction.

It is proposed that spin-crossing effects can dramatically affect reaction mechanisms, rate constants, branching ratios, and temperature behaviors of organometallic transformations. This phenomenon is termed two-state reactivity (TSR) and involves participation of spin inversion in the rate-determining step. While the present analysis is based on studies of transition metals under idealized conditions, several recent reports imply that TSR is by no means confined to the gas phase. In fact, participation of more than a single spin surface in the reaction pathways is proposed as a key feature in organometallic chemistry.

Two-State Reactivity as a New Concept in Organometallic Chemistry§

Organometallic chemistry in the gas phase

The phenyl cation is known to have two low-energy minima, corresponding to 1
A
1 and 3
B
1 states, the first of which is more stable by ca. 25 kcal/mol. The minimum energy crossing point between these two surfaces, located at various levels including a hybrid method first described here, lies just above the minimum of the triplet, 0.12 kcal/mol at the CCSD(T)/cc-pVDZ//B3LYP/SV level, and there is significant spin-orbit coupling between the surfaces at this point. On the basis of these results, the lifetime of the triplet is expected to be very short.

The singlet and triplet states of phenyl cation. A hybrid approach for locating minimum energy crossing points between non-interacting potential energy surfaces

Gas-phase experiments with state-of-the-art techniques of mass spectrometry provide detailed insights into numerous elementary processes. The focus of this Review is on elementary reactions of ions that achieve complete catalytic cycles under thermal conditions. The examples chosen cover aspects of catalysis pertinent to areas as diverse as atmospheric chemistry and surface chemistry. We describe how transfer of oxygen atoms, bond activation, and coupling of fragments can be mediated by atomic or cluster metal ions. In some cases truly unexpected analogies of the idealized gas-phase ion catalysis can be drawn with related chemical transformations in solution or the solid state, and so improve our understanding of the intrinsic operation of a practical catalyst at a strictly molecular level.

Gas-phase catalysis by atomic and cluster metal ions: the ultimate single-site catalysts.

Four seemingly simple transformations related to the chemistry of methane will be addressed from mechanistic and conceptual points of view: 1) metal-mediated dehydrogenation to form metal carbene complexes, 2) the hydrogen-atom abstraction step in the oxidative dimerization of methane, 3) the mechanisms of the CH(4)→CH(3)OH conversion, and 4) the initial bond scission (C-H vs. O-H) as well as the rate-limiting step in the selective CH(3)OH→CH(2)O oxidation. State-of-the-art gas-phase experiments, in conjunction with electronic-structure calculations, permit identification of the elementary reactions at a molecular level and thus allow us to unravel detailed mechanistic aspects. Where appropriate, these results are compared with findings from related studies in solution or on surfaces.

Helmut Schwarz

Papers

Two-State Reactivity as a New Concept in Organometallic Chemistry§

Organometallic chemistry in the gas phase

The singlet and triplet states of phenyl cation. A hybrid approach for locating minimum energy crossing points between non-interacting potential energy surfaces

Gas-phase catalysis by atomic and cluster metal ions: the ultimate single-site catalysts.

Chemistry with Methane: Concepts Rather than Recipes