Chapter 6. Calculation of physical and chemical properties of nanomaterials. (2 hours).

1. Chapter 1. Introduction, perspectives, and aims. On the science of simulation and modelling. Modelling at bulk, meso, and nano scale. (2 hours). Chapter 2. Experimental Techniques in Nanotechnology. Theory and Experiment: “Two faces of the same coin” (2 hours). Chapter 3. Introduction to Methods of the Classic and Quantum Mechanics. Force Fields, Semiempirical, Plane-Wave pseudopotential calculations. (2 hours) Chapter 4. Intoduction to Methods and Techniques of Quantum Chemistry, Ab initio methods, and Methods based on Density Functional Theory (DFT). (4 hours) Chapter 5. Visualization codes, algorithms and programs. GAUSSIAN, CRYSTAL, and VASP. (6 hours). .

2. . Chapter 6. Calculation of physical and chemical properties of nanomaterials. (2 hours). Chapter 7. Calculation of optical properties. Photoluminescence. (3 hours). Chapter 8. Modelization of the growth mechanism of nanomaterials. Surface Energy and Wullf architecture (3 hours) Chapter 9. Heterostructures Modeling. Simple and complex metal oxides. (2 hours) Chapter 10. Modelization of chemical reaction at surfaces. Heterogeneous catalysis. Towards an undertanding of the Nanocatalysis. (4 hours)

3. Chapter 2. Experimental Techniques in Nanotechnology. Theory and Experiment: “Two faces of the same coin” Juan Andrés y Lourdes Gracia Departamento de Química-Física y Analítica Universitat Jaume I Spain & CMDCM, Sao Carlos Brazil Sao Carlos, Novembro 2010

4. Experiment and Theory: New strategies and methodologies Simulation Oxford Dictionary Definition “… produce a computer model of (a process) “

5. Powerful and indispensable tools for nanoscience/nanotechnology SYNTHESIS Obtaining tiny slabs that serve as precisely controlled mockups of the real world catalysts. • Vapor Liquid Solid (VLS) • Chemical Vapor deposition (CVD) • Solid Vapor Deposition (SVD) • Single Source Chemical Vapor Deposition (SSCVD) • Litography • Laser Ablation • Sol-Gel • Template-Assisted Methods

6. M. L. Curri, R. Comparelli, M. Striccolia and A. Agostiano Phys. Chem. Chem. Phys., 2010, 12, 1119

7. Powerful and indispensable tools for nanoscience/nanotechnology EXPERIMENTS • Scanning Tunneling Microscopy (STM) • Scanning Electron Microscopy (SEM) • Energy-Dispersive X-ray Spectroscopy (EDX) • Transmission Electron Microscopy (TEM) • Selected Area Electron Diffraction (SAED) • X-ray Photoelectron Spectroscopy (XPS) • Powder X-ray Diffraction (XRD) • Electron Energy Loss Spectroscopy (EELS) • Raman Spectroscopy • Photolumuniscence (PL) • Cathodoluminiscence (CL)

8. In the last 30 years, we have seen an extraordinary experimental advance on the techniques to produce, in a controlled way, smaller and smaller structures, even in atomic scale. Parallel to these achievements, characterization techniques have also matured in order to better understand the properties of these materials. Altogether, these factors are responsible for the rising of nanoscience and nanotechnology. Schwartz, D. A.; Norberg, N. S.; Nguyen, Q. P.; Parker, J. M.; Gamelin, D. R. J. Am. Chem. Soc. 2003, 125, 13205. Peng, X.; Manna, L.; Yang, W.; Wickham, J.; Scher, E.; Kadavanich, A.; Alivisatos, A. P. Nature 2001, 404, 59. Shevchenko, E. V.; Talapin, D. V.; Murray, C. B.; O’Brien, S. J. Am. Chem. Soc. 2006, 128, 3620

9. Powerful and indispensable tools for nanoscience/nanotechnology Last but not least, theorists are employing ab initio schemes or density functional theory to calculate how molecules will stick to the nanoparticles and interact. THEORY

10. History (1) All of Chemistry revolves around swapping electrons, and theoretical and computational methods and techniques forecasting how atoms and molecules will rearrange themselves and bond as the electrons they share shift to minimize energy.

11. History (2) G.Whitesides What Will Chemistry Do in the Next Twenty Years? Angew. Chem Int. Ed. Engl., 29, 1209 (1990)

12. The path of Chemistry in the future will be determined by its generation of new ideas through four basic research Areas .Materials Chemistry .Biological Chemistry .Computational Chemistry .Chemistry exploring the limits of size and speed in chemical phenomena

13. Materials Chemistry Polymers Surfaces and Interfaces Functional and “smart”materials Materials for manufacturing Environmentally compatible materials Biological Chemistry Molecular recognition Evolution and self-assembly Bioenergetics Chemistry exploring the limits of size and speed in chemical phenomena. Exploring the limits : very small; very fast; very large Computational Chemistry Increasing power New architectures: massively parallel machines and neural nets

14. Somorjai, G. A.; Levine, R. D. “The Changing Landscape of Physical Chemistry at the Beginning of the 21st Century” J. Phys. Chem. B 109, 9853 (2005). “Now enter the nanosciences, which again are also driven by the needs of technologies, which provide challenges to learn themanipulation of matter on the nanoscale: connecting molecules and studying their self-assembly, optical, chemical, electronic, magnetic, and mechanical properties. The centralizing themes of physical chemistry again become dominant at the start of the 21st century, just as they were dominant in the early decades of the 20th century.” “There are major changes occurring in the way research is performed in physical chemistry. This is in part due to our success in providing an ever-increasing science component to existing and emerging technologies that accelerates their need for even more. Our ability to study the science of chemical complexity permitted us to target major scientific and societal problems that requirean interdisciplinary approach” “These include environmental chemistry, problems of size reduction in microelectronics that led to the rise ofnanoscience and nanotechnologies, and the design of drugs and implant devices that extend human life span and sustain the health of the human body.”

15. THE ROYAL SWEDISH ACADEMY OF SCIENCES The discovery of carbon atoms bound in the form of a ball is rewarded Nanostructures 1996

16. THE ROYAL SWEDISH ACADEMY OF SCIENCES Development of computational methods in chemistry awarded Quantum Chemistry 1998

17. THE ROYAL SWEDISH ACADEMY OF SCIENCES Femtochemistry 1999 For showing that it is possible with rapid laser technique to see how atoms in a molecule move during a chemical reaction.

18. “Chemistry is not solely an experimental science anymore”

19. Nobel Prize in Physics 2010 Andre Geim and Konstantin Novoselov for their "groundbreaking experiments regarding the two-dimensional material graphene

21. M. Pumera, Chem. Soc. Rev., 2010, 39, 4146–4157

22. Nobel Prize in Chemistry 2010 Richard F. Heck, Ei-ichi Negishi, and Akira Suzuki winners for "developing new, more efficient ways of linking carbon atoms together to build the complex molecules that are improving our everyday lives."

23. This was a reaction that was possible with other metals, but it did not work very well. With palladium it worked much better. One of the main features of the reactions is that they are catalytic processes that allow synthetic chemists to do things which they could not previously do - to join carbon atoms together in a new way,'

24. To illustrate the diversity and importance of the palladium-catalysed cross coupling reactions: • - Total synthesis of the anticancer drug Taxol (paclitaxel) • The Heck reaction is also used to make a strategic bond in a synthesis of morphine. • - Negishi coupling was key to the laboratory synthesis of the natural product hennoxazole A, a marine antiviral compound. • - Suzuki coupling is used to prepare the antiviral bromoindole alkaloid dragmacidin. • These are merely a handful of examples of palladium-catalysed cross coupling, which has been used - and continues to be used - in the synthesis of thousands of important compounds, from the most complex natural products to tonne-scale industrial intermediates.

25. “Over the last years, first-principles calculations have become recognized as an outstanding tool so as to elucidatethe electronic structure of crystalline materials”

26. “Theory and experimentation combine today in the search for understanding of the inner structure of matter” W. Kohn, Rev. Mod. Phys, 1999, 71, 1253 (Nobel Lecture) Electronic structure of matter-wave functions and density functionals “.....for his development of the density-functional theory.....” J. A. Pople, Rev. Mod. Phys, 1999, 71, 1267 (Nobel Lecture) Quantum chemical models “.....for his development of computational methods in quantum chemistry.....”

27. Basic Challenges Since chemistry concerns the study of properties of substances or molecularsystems in terms of atoms, the basic challenge facing computational chemistry is to describe or even predict. 1. the structure and stability of a molecular system. concerns prediction of which state of system has the lowest energy. 2. the (free) energy of different states of a molecular system. involves prediction of the relative (free)energy of different states. 3. reaction processes within molecular systems in terms of interactions at the atomic level. involves prediction of the dynamic process of change of states. 1 < 2 < 3 Increasing difficulty

28. Theory vs. Experiment Modern research in the chemical sciences seeks not only to make useful molecules and materials but to understand, design, and control their properties. Theory is at the very center of this effort, providing the framework for an atomic and molecular level description of chemical structure and reactivity that forms the basis for interpreting experimental data and provides guidance toward new experimental directions. Theoretical and computational chemistry has developed into an important tool in almost all areas of chemistry. Their methods and techniques have found its way into the everyday work of many experimental chemists. Calculations can predict the outcome of chemical reactions, afford insight into reaction mechanisms, and be used to interpret structure and bonding in molecules. Thus, contemporary theory offers tremendous opportunities in experimental chemical research.

29. Theory vs. Experiment Combined experimental and computational studies of chemical reactivity can yield remarkable insight into reaction mechanisms and kinetics. This is particularly true for chemical reaction taking place in very tight places, involving unusual mechanistic features. Physics-based simulations complement experiments in building a molecular-level understanding: they can test hypotheses and interpret and analyse experimental data in terms of interactions at the atomic level not available experimentally. The joint use of both theoretical and experimental results also suggests additional experiments and simulations that can further increase our knowledge. The insights gained from simulation are synergistic with those that arise from new experiments, and sometimes they lead the way on problems where experiments are not available.

30. Feymann, R. P. Eng. Sci.23, 22 (1960). “The principle of Physics as far as I can see, do not speak against the possibility of maneuvering things atom by atom .” Quantum Mechanics Theoretical and Computational Chemistry

31. Fundaments Methods Techniques Classical Statistical Mechanics Quantum Mechanics THEORETICAL AND COMPUTATIONAL CHEMISTRY

32. CRYSTALINE SOLID STATE LIQUID STATE MACROMOLECULES GAS PHASE Quantum Mechanics Possible Possible Easy Classical Statistical Mechanics Easy Trivial Easy REDUCTION to few particles by dilution Essential many-particle system REDUCTION to the few degrees of freedom by symmetry Classification of Molecular Systems

33. Points 1. 2. & 3. allows us to say “we can actually start to observe phenomena at the atomic scale under realistic conditions.” The dream of Richard P. Feynman (in 1960’s) is fulfilled!

34. of chemical species of difficult (in some cases) experimental detection Methods & Techniques of Theoretical and Computational Chemistry • Prediction • Interpretation • Characterization • Understanding physical and chemical properties at atomic level

35. Computational and Theoretical Chemistry - Energy (DE, DG, DH and DS) - Ionization potential (IP) - Electron affinity (EA) - Geometry (bond distance, bond angle and dihedral angle) - Electronic properties (molecular orbitals, density of states, band gap) - Vibrational Frequencies, IR (analysis of stationary points; R, P, I and TS structures) - Analysis of Potential Energy Surfaces (crossing points, valley ridge inflexion points, conical intersections) - Electron density (topological analysis: AIM, ELF)

36. Computational and Theoretical Chemistry Software GAUSSIAN (2009) CRYSTAL (2009) VASP GAMESS MOLCAS ADF XcrysDen TopMod Hardware Silicon Graphics MIPS R14k 400MHz PC/Linux Cluster, AMD +2200MP

37. Theoretical work Experimental work complementary tools The cooperation between both worlds is mandatory

38. Interaction between Experiments, Analytical Theories, and ComputationR. A. Marcus, J. Phys. Chem. C 2009, 113, 14598–14608 • We all recognize that one of the main goals in research is to capture the physical essence of a phenomenon and use it not only to interpret but also to predict the results of new experiments. One view of theory, demonstrated in the present article, is that experiments are primary, often the source of new theory, and that the interaction of theory and experiment is paramount, each stimulating the other. • Nevertheless, discerning basic theoretical problems in the wealth of available experimental and computational results can be a major hurdle and sometimes the development of the theory can be relatively rapid once the existence of an experimental puzzle is known. The writer continues to be impressed with this exciting interplay of experiment and theory and with many experimental puzzles that exist and that continue to arise in new experiments, when one keeps an eye out for them. For the theoretically oriented students it is perhaps a truism to add that the broader one’s background is in physics, chemistry and mathematics, and the more one is familiar with the new results and the potential and limitations of new techniques, the larger the range of interesting problems that one can address.

39. Experiment and Theory in Harmony Mark A. Johnson at Yale University discusses how the two sides of physical chemistry have necessarily developed together, and looks at how their synergy dictates the direction of contemporary research. Equations such as Schrödinger’s famous contribution to quantum mechanics underpin much of physical chemistry. Nature Chemistry, 1, 8 (2009)

40. Experiment and Theory in Harmony Physical chemists seek to anchor the empirical rules of chemistry to the laws of physics, and thus provide secure concepts to explain the trends seen in reactivity and molecular structure. A recurrent theme in contemporary physical chemistry is a convergence of experimental and theoretical methods towards sufficiently complex model systems. By this I mean systems that not only reproduce ‘real’ chemical processes but also do so in a fashion that reveals molecular level, quantum-mechanically consistent pictures that are not greatly obscured by either thermal or ensemble averaging. Nature Chemistry, 1, 8 (2009)

45. Controlling the properties of nanostructures requires a detailed understanding of structure, microstructure, and chemistry at ever-decreasinglength scales. The modern day transmission electron microscope has thus become an indispensable tool in the study of nanostructures. In this Perspective,we present a brief account of the capabilities of the TEM with some typical examples for characterizing nanostructures. The modern-day TEM has moved from a simple characterization tool to a nanoscale laboratory enabling in situ observation of several fundamental processes at unprecedented resolution levels. N. Ravishankar, J. Phys. Chem. Letters, 2010, 1, 1212–1220

48. The future of nanotechnology rests upon approaches to making new, useful nanomaterials and testing them in complex systems. Currently, the advance from discovery to application is constrained in nanomaterials relative to a mature market, as seen in molecular and bulk matter. To reap the benefits of nanotechnology, improvements in characterization are needed to increase throughput as creativity outpaces our ability to confirm results. The considerations of research, commerce, and regulation are part of a larger feedback loop that illustrates a mutual need for rapid, easy, and standardized characterization of a large property matrix. Now, we have an opportunity and a need to strike a new balance that drives higher quality research, simplifies commercial exploitation, and allows reasoned regulatory approaches. Erik K. Richman and James E. Hutchison VOL. 3 ▪ NO. 9 ▪ 2441–2446 ▪ 2009

50. Techniques for nanoscale structure determination Surface science techniques are characterized by their ability to provide sensitivity to a slice of material with nanoscale thicknesson top of a single-crystal substrate. The blossoming of nanoscience and nanotechnology requires adapting or developing appropriate techniques of characterization with additional nanoscale resolution in one or two of the other dimensions. The challenge of detailed atomic-level structure (bond lengths and bond angles) in such nanomaterials is even more formidable, especially if we wish to keep a three-dimensional spatial resolution in a single nanoparticle.