Manuel Azaña:

1. La misión de la UNIVERSIDAD es el desarrollo social, económico y cultural de la sociedad de su entorno a traves de la creación y transmisión de CONOCIMIENTOS, ofreciendo una docencia de calidad y desarrollando una investigación avanzada de acuerdo con exigentes criterios internacionales.

2. José Ortega y Gasset acuñó una metáfora sumamente útil para comprender intuitivamente la situación de nuestro tiempo: La cultura es el esfuerzo permanente que un nadador realiza para mantenerse a flote.

3. Manuel Azaña: Si cada español hablara de lo que sabe y solo de lo que sabe, se haría un gran silencio nacional que podríamos aprovechar para estudiar

4. The large investments in research and education made in recent years have provided Brazilian scientists with the conditions to achieve scientific excellence. NATURE MATERIALS | VOL 9 | JULY 2010 |527 WWW.NATURE.COM/NATUREMATERIALS

6. W.J. Parak, ACS Nano, 4, 4333 (2010) Nanoscience research crosses disciplines and has incorporated knowledge from many fields

7. Theoretical and Computational Nanotechnology: Fundaments and Applications. Prof. Juan Andrés Dr. Lourdes Gracia

8. Juan Andres Bort Work address: Department of Physical and Analytical Chemistry, UniversitatJaumeI,Castelló(Spain) Graduation: Chemistry, 1978, Universitat de Valencia Ph.D. dissertation: Chemistry,1982, Universitat de Valencia Current position: 1994, Full Professor, Physical Chemistry, UniversitatJaume I • ACADEMIC MANAGEMENT • - Director of International relationships (2 years) • Director of the Department of Experimental Sciences (7 years) • Vice-rector of Scientific and Technological Promotion, Universitat Jaume I (5 years) PUBLICATIONS - Articles: 292 published + 7 submitted for publication. - Books: 15 published (text books) - Book Chapters: 9 published (research) - 2 published Book as Co-editor

9. MAIN LINES OF RESEARCH Electronic structure and chemical reactivity. Molecular mechanics of chemical reactions. Enzyme Catalysis: Quantum Mechanics (QM)/Molecular Mechanics(MM) and Molecular Dynamics studies. Theoretical organic, organometallic and biological chemistry. Topological analysis of electronic distribution. Electric and magnetic properties of materials. High pressure effects in materials. Growth, crystallization and formation processes in crystals. Optical properties of materials. Diffusion processes in solid state • Theses supervised: 18 Ph. D. - More than 40 research projects as principal research, funded by European Community, Ministerio de Educación y Ciencia, Generalitat Valenciana, Fundación Bancaixa-UJI - More than 200 Communications at both national and international congresses - h index= 35, more than 4300 citations.

10. Lourdes Gracia Edo Work address: Department of Physical and Analytical Chemistry, UniversitatJaume I, Castelló ( Spain) Graduation: Chemistry, 1999, UniversitatJaume I Ph.D. dissertation: Chemistry, 2005, UniversitatJaume I Current position: PostDoc Researcher, Physical Chemistry, UniversitatJaume I MAIN LINES OF RESEARCH Electronic structure and chemical reactivity. High pressure effects in materials. Growth, crystallization and formation processes in crystals. Electric and optical properties of materials. Diffusion processes in solid state - Articles: 24 published + 3 submitted for publication. - Participation in 13 research projects, funded Ministerio de Educación y Ciencia, Generalitat Valenciana, Fundación Bancaixa-UJI - 20 Communications and Poster presentation at both national and international congresses

11. Acknowledgments Dr. Mario Moreira Diogo Volanti Dr. Valeria Longo Dr. Elaine Paris Dr. Marcelo Orlandi Prof. Jose A. Varela Prof. Elson Longo Prof. Edson Leite (CMDCM, Sao Carlos and Araraquara, Brazil) Prof. Armando Beltrán Universitat Jaume I Dr. Julio Sambrano (Bauru) Dr. Fabricio Sensato (Sao Paulo) Daniel Stroppa (Campinas) Brazilian agencies Fapesp and CNPq by the financial support,. Research funds provided by the Ministerio de Educación y Cultura of the Spanish Government. Docent Stay supported by Universitat Jaume I-Banco Santander

12. 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 pseudpotential 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). .

13. . 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)

14. Chapter 1. Introduction, perspectives, and aims. On the science of simulation and modelling. Modelling at bulk, meso, and nano scale. Juan Andrés y Lourdes Gracia Departamento de Química-Física y Analítica Universitat Jaume I Spain & CMDCM, Sao Carlos Brazil Sao Carlos, Novembro 2010

15. How computational/theoretical chemists can be useful in the field of nanoscience/nanotechnology?

16. What can a theoretical/computational chemist bring to the experimentalist active in the devolopment of nanoscience/nanotechnology ?

17. General Considerations 1 An overview of some of the theoretical questions that remain to be answered, is a useful first step towards designing new fundamental research programs (combining both experimental and theoretical investigations).

18. General Considerations 2 I hope that this original approach will be useful to experimentalists wishing to carry out fundamental studies of nanostructures, and to theoreticians who are looking for new challenges.

19. General Considerations 3 It should be emphasized that this problem area is not just of academic interest. All the questions mentioned above have direct relevance for different physical and chemical phenomena.

20. General Considerations 4 This course provides an exemplary overview of research on this topic, from simple model systems where first qualitative explanations start to be successful, up to more realistic complex systems which are still beyond our understanding.

21. Outline • Introduction • Nanoscience, Nanotechnology • History • Methods of Theoretical & Computational Chemistry • Challenges

22. Nature has evolved highly complex and elegant mechanisms for materials and synthesis. Living organisms produce materials with physical properties that still surpass those of analogous synthetic materials with similar phase compositions. Nature has long been using the bottom-up nanofabrication method to form self-assembled nanomaterials that are much stronger and tougher than many man-made materials formed top-down.

23. The term “nano” is derived from the Greek word for “dwarf”, “nanos”. This etymology, and its placement on the metric scale (1 nm=10-9 m), make it clear that tiny dimensions not visible to the naked eye, beyond the normal limits of our observation, are involved. Approaching it from familiar terrain may make the “nanoworld” more easily accessible (Figure 1).

26. Characteristic of nanoparticles, besides their small size, is their vast surface area. A simple thought experiment will serve to illustrate this concept (Figure 2). Take a cube with edges 1 cm in length—roughly the size of a sugar cube—at divide it step by step into cubes with edges 1 nm in length. While the sum of the volumes remains the same, the number of individual cubes and their total surface area increases dramatically. The surface area of the 1021 “nanocubes”, at 6000 m2, amounts to roughly the area of a football field (ca. 7000 m2)—created from a single sugar cube! Compared to an infinite three-dimensional solid (aptly expressed by the term “bulk”), with nanoparticles we may expect that their physicochemical properties are strongly influenced, if not indeed dominated, by the surface. Unsaturated bonding sites and unoccupied coordination sites will play a major role, compared to a highly ordered crystalline solid

27. Dominance of broken bonds and nonbonding electrons at the nanoscale, Chang Q Sun, Nanoscale, 2010 Materials at the nanoscale demonstrate novel properties of two types. One is the size and shape induced tunability of the otherwise constant quantities associated with bulky species. For example, the elastic modulus, dielectric constant, conductivity, melting point, etc, of a substance no longer remain constant but change with its shape and size; the other is the emergence of completely new properties that cannot be seen from the bulk such as the extraordinary high capability for catalysis, nonmagnetic–magnetic and conductor–insulator transitions. These two entities form the foundations of nanoscience and Nanotechnology that has been recognized as one of the key drivers of science, technology and economics in the 21st century.

28. Nanoscience 1 Originating from the fields of physics, chemistry, materials science, and chemical engineering, this area of study is now often referred to as nanoscience.

29. Nanoscience 2 Nanostructured materials such as nanoparticles, nanotubes, nanowires (nanorods), nanoribbons (nanobelts), nanotapes, nanorings, nanoplates, nanotriangles, nanosheets, nanoballs and nanohelices,

30. Nanoscience 3 ALL IS NANO ! …..have attracted extensive attention due to their properties with important and potential applications in constructing nanoscaled electronic and opto-electronic devices, gas sensors, catalysts, and thin growth.

31. 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.”

32. Where are we? • TODAY THE QUEST FOR NOVEL MATERIALS WITH DISTINCT PROPERTIES FOR CRITICAL TECHNOLOGICAL APPLICATIONS HAS MOTIVATED A CONSITENT EFFORT IN BETTER UNDERSTANDING SOLID-STATE PROCESSES, BOTH EXPERIMENTALLY AND FROM THEORY • THE PROGRESS OF THE PAST DECADES ON NANOMATERIALS HAVE SHOWN THAT BULK PROPERTIES BREAK DOWN ON CROSSING LOWER SIZE LIMITS, UNFOLDING A RICH SET OF NEW PHYSICAL AND CHEMICAL PROPERTIES AND OPENING NEW SYNTHETIC ROUTES • FOR THE SYNTHETIC EFFORTS TO FULLY TAKE ADVANTAGE OF SUCH PECULIAR PROPERTIES, A PRECISE AND FIRM ATOMISTIC UNDERSTANDING IS MANDATORY • SIMULATIONS OF REAL MATERIALS UNDER CONDITION CORRESPONDING TO THE EXPERIMENTS ARE SHEDDING LIGHT ONTO YET ELUSIVE ASPECTS • ACCORDINGLY, A NEW WAY OF BRIGING TOGETHER THEORY, IMPLEMENTATION OF SIMULATION STRATEGIES AS A POWEFUL SUPPORT TO THE EXPERIMENTS IS EMERGING.

33. Where are we? • THE DEVELOPMENT AND IMPLEMENTATION OF FIRST-PRINCIPLE METHODS AND TECHNIQUES ALLOW TO CARRY OUT CALCULATIONS TO QUANTITATIVELY PREDICT AND EXPLAIN THE PHYSICAL AND CHEMICAL PROPERTIES OF MATERIALS. • ELECTRONIC STRUCTURE THEORY PROVIDES BOTH CONCEPTUAL UNDERSTANDING AND COMPUTATIONAL TOOLS TO CALCULATE IT. • ADVANCE IN THEORETICAL METHODS AND TECHNIQUES AS WELL AS COMPUTATIONAL POWER HAVE HAD A TREMENDOUS IMPACT IN MATERIALS SCIENCE • OF COURSE, THEORETICAL GUIDANCE NEEDS TO BE USED IN A COOPERATIVILY MANNER WITH THE ACCUMULATED EXPERIENCE OF EXPERIMENTAL EXPLORERS.

34. Where are we? • DURING THE LAST YEARS ELECTRONIC STRUCTURE THEORY DEVELOPED FROM A DESCRIPTIVE TO AN ANALYTICAL TOOL AND IS NOW AN INTEGRAL PART OF RESEARCH WITH IMPORTANT CONSEQUENCES: • 1. FACILITING THE INTERPRETATION AND RATIONALIZATION OF EXPERIMENTAL RESULTS • 2. HELPING TO UNCOVER ESSENTIAL CRYSTAL STRUCTURE-PROPERTY RELATIONSHIPS • 3. DIRECTING FURTHER

35. Computer simulation methods in physical chemistry: Large molecules, fluids and solids Annual Meeting of the Deutsche Bunsen-Gesellschaft für Physikalische Chemie, Stuttgart, May 24-26, 2001 “Science is undergoing a structural transition from two broad methodologies to three, namely from experimental and theoretical science to include the additional category of computational and information science. A comparable example of such a change occurred with the development of systematic experience science at the time of Galileo” — Advanced Scientific Computing Committee of the US National Science Foundation. J. Brickmann and J. Sauer, Phys. Chem. Chem. Phys., 2001, 3

36. In silico methods are a valid tool for analysing the properties of materials and interest in computational modelling techniques to predict their physical/chemical properties is constantly growing.

37. Real Word Model of the Word Experiment Theory Applying Theoretical Methods, Computing Techniques and Mathematical Algorithms Classification Abstraction Simplification Approximation Generalization Simulation Experimental Data Predictions Comparing is testing

38. Three Important Turns in Science Modified from: van Gunsteren et al., Angew. Chem. Int. Ed. Engl, 45, 4064 (2006) Thales 600 BC ObserveModel Galileo 1500 BC Model  Design Experiment  ObserveModel Rahman and Parrinello Mimic Reality on a Computer  ObserveModel “Crystal Structure and Pair Potentials. A Molecular Dynamics Study” Physical Review Letters, 45, 1196 (1980)

39. “Computations on complex systems are, in my opinion, the current frontier of theoretical chemistry” D. G. Truhlar Molecular Modeling of Complex Chemical Systems J. Am. Chem. Soc., 2008, 130, 16824-16827 39

40. “THE ETERNAL MISTERY OF THE WORLD IS ITS COMPREHENSIBILITY. THE FACT THAT IT IS COMPREHENSIBLE IS A MIRACLE” ALBERT EINSTEIN

41. CLUSTER-ASSEMBLED MATERIALS Fullerenes, atomic clusters, and larger inorganic nanocrystals can be used as assembly elements for creating materials with tailored properties. S. A. Claridge, A. W. Castleman, S. N. Khanna, C. B. Murray, A. Sen, P. S. Weiss, ACS Nano2009, 3, 244. 41

42. SHAPE-CONTROLLED SYNTHESIS OF METAL NANOCRYSTALS Reaction pathways that lead to fcc metal nanocrystals having different shapes. First, a precursor is reduced or decomposed to form the nuclei (small clusters). Once the nuclei have grown past a certain size, they become seeds with a single-crystal, singly twinned, or multiply twinned structure. If stacking faults are introduced, then plate-like seeds will be formed. 42 Y. Xia, Y. Xiong, B. Lim, Sara E. Skrabalak, Angew. Chem. Int. Ed. 2009, 48, 60.

44. Microscopic and macroscopic behaviors of nanoparticles depend on a number of a number of important characteristics and properties V. H. Grassian J. Phys. Chem. C 2008, 112, 18303

45. A. Greenberg VOL. 3 ▪ NO. 4 ▪ 762 ▪ 2009

50. The world today is facing increasing energy demands and simultaneously demand for cleaner and more environmentally friendly technologies. The development of new nanomaterials is expected to have a major impact on the development of novel sustainable energy technologies. - Bérube, V.; Radtke, G.; Desselhaus, M.; Chen, G. Size Effects on the Hydrogen Storage Properties of Nanostructured Metal Hydrides: A Review. Int. J. Energy Res. 2007, 31, 637. - Bérube, V.; Chen, G.; Dresselhaus, M. S. Impact of Nanostructuring on the Enthalpy of Formation of Metal Hydrides. Int. J. Hydrogen Energy 2008, 33, 4122. Schlapbach, L.; Zu¨ ttel, A. Hydrogen-Storage Materials forMobile Applications. Nature 2001, 414, 353. - Eberle, U.; Felderhoff, M.; Schüth, F. Chemical and Physical Solutions for Hydrogen Storage. Angew. Chem., Int. Ed. 2009, 48, 6608. - Orimo, S.; Nakamori, Y.; Eliseo, J. R.; Zuüttel, A.; Jensen, C. M. Complex Hydrides for Hydrogen Storage. Chem. Rev. 2007,107, 4111. - Dornheim, M.; Eigen, N.; Barkhordarian, G.; Klassen, T.; Bormann, R. Tailoring Hydrogen Storage Materials towards Application. Adv. Eng. Mater. 2006, 8, 377.