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

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: 305 published + 7 submitted for publication. - Books: 15 published (text books) - Book Chapters: 10 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 h index= 37, more than 4600 citations.

10. 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 400 communications at both national and international congresses. • More than 20 as Invited Speaker in international congresses and 5 in national congresses. • 5 as Chairman in international congresses and 2 in national congresses. • 15 Conferences in different Universities of Brazil, Chile, France, Italy and Sweden. • 14 Conferences in different Universities of Spain (Barcelona, Cádiz, Gerona, Granada, La Coruña, Madrid, Oviedo, País Vasco, Santiago de Compostela, Sevilla, Valencia, Zaragoza) .

11. Acknowledgments Dr. Mario Moreira Dr. DiogoVolanti Dr. Valeria Longo Dr. Marcelo Orlandi Prof. Jose A. Varela Prof. Elson Longo Prof. EdsonLeite (CMDCM, Sao Carlos and Araraquara, Brazil) Prof. Armando Beltrán Dr. Lourdes Gracia (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 UniversitatJaume I-BancoSantander

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 Departamento de Química-Física y Analítica Universitat Jaume I Spain & CMDCM, Sao Carlos Brazil Sao Carlos, Octubro 2011

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. “It is the goal of this Course to present in one place the key features, methods, tools, and techniques of Theoretical and Computational Nanotechnology, to provide examples where Theoretical and Computational Chemistry has produced a major contribution to multidisciplinary efforts, and to point out the possibilities and opportunities for the future.” “Maybe it is because I work on quantummechanics, but I think that the bigchallenge in materials science in general as well as in Naoscience and Nanotechnology in particular is understanding how quantum mechanics influences materials at the microscopic level.”

18. Simulation techniques are playing an increasingly important role in the burgeoning field of nanotechnology. Arguably the nanotechnology revolution, which has seen a worldwide investment of more than $42 billion dollars over the last decade, was seeded both by developments in analytical techniques capable of characterising down to the nanoscale and by developments in computational hardware and techniques capable of modelling structures at that length scale. Atomistic simulation (molecular mechanics and dynamics, quantum mechanics and field based approaches) has played an important role in nanoscience: predicting nanostructure and revealing mechanisms for intriguing nanoscale behaviors. Experimental nanoscience has provided a valuable source of data for the validation of simulation techniques, basis sets and force-fields. As nanoscience is increasingly turned into nanotechnologies, computer simulation methods can play a critical role.

19. Experimental nanoscience has provided a valuable source of data for the validation of simulation techniques, basis sets and force-fields. As nanoscience is increasingly turned into nanotechnologies, computer simulation methods can play a critical role.

20. 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).

21. 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.

22. 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.

23. 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.

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

25. 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.

26. 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).

29. 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

30. A nanomaterial is commonly defined as an object with dimensions of 1–100 nm, which includes nanogels, nanofibers, nanotubes and nanoparticles (i.e. spheres, rods and cubes). NMs can have various applications in areas such as electronics, clothing, food packaging, paint, surface modifications, additives in food packaging and drugs. It is expected that the sale of products employing nanotechnology may reach $1 trillion per year by 2015, with medical-related products alone occupying $53 billion in this market. In August 2009, there were more than 1000 nanotechnology incorporated products marketed by 485 companies in 24 countries. W. W. I. C. f. Scholars, Consumer Products: An Inventory of Nanotechnology-based Consumer Products Currently on theMarket, 2010, http://www.nanotechproject.org/inventories/consumer/, T. Xia, N. Li and A. E. Nel, Annu. Rev. Public Health, 2009, 30,137. C. F. Jones and D. W. Grainger, Adv. Drug Delivery Rev., 2009, 61, 438.

31. Nanomaterials are of immense importance in today’s modern society. The development of chemical industries, environmental protection and new-energy resources (e.g., fuel cells, lithium ion batteries) have long relied on nanomaterials with exceptional properties. The fields of catalysis, electrocatalysis, photocatalysis and photoelectricity are all examples of where nanotechnology is impacting on current science.1–4 1 C. Burda, X. B. Chen, R. Narayanan and M. A. El-Sayed, Chem. Rev., 2005, 105, 1025. 2 M. Haruta, CATTECH, 2002, 6, 102. 3 D. Astruc, F. Lu and J. R. Aranzaes, Angew. Chem., Int. Ed., 2005, 44, 7852. 4 M. C. Daniel and D. Astruc, Chem. Rev., 2004, 104, 293.

32. As particle dimensions reduce towards the nanoscale, the surface-to-volume ratio proportionally increases and smallsize effects associated with nanoparticles become more pronounced. Understanding the nanoscale topography of surface sites, such as terraces, steps, kinks, adatoms and vacancies, and their effects on catalytic and other physicochemical properties is the key to designing nanoscale functional materials by nanotechnology.5–7 5 G. A. Somorjai, Science, 1978, 201, 489. 6 F. Tao and M. Salmeron, Science, 2011, 331, 171. 7 D. L. Feldheim, Science, 2007, 316, 699.

33. The performance of nanocrystals used as catalysts depends strongly on the surface structure of facets enclosing the crystals. Thermodynamics usually ensures that crystal facets evolve to have the lowest surface energy during the crystal growth process. For a pure metal, the surface energy relies on coordination numbers (CNs) of surface atoms as well as their density. For example, it increases in the order of g{111} < g{100} < g{110} < g{hkl} on a face-centered cubic (fcc) metal, where {hkl} represents high-index planes with at least one Miller index larger than 1.8,9 8 Z. L. Wang, J. Phys. Chem. B, 2000, 104, 1153. 9 Y. N. Wen and H. M. Zhang, Solid State Commun., 2007, 144, 163.

34. For a metal oxide, the surface energy increases with increasing density of dangling bonds. Generally, high-energy surfaces have an open surface structure and possess exceptional properties. Long-term fundamental studies in surface science have shown that Pt high-index planes with open surface structure exhibit much higher reactivity than that of (111) or (100) low-index planes, because high-index planes have a large density of low-coordinated atoms situated on steps and kinks, with high reactivity required for high catalytic activity.10–12 10 N. P. Lebedeva, M. T. M. Koper, J. M. Feliu and R. A. van Santen, J. Phys. Chem. B, 2002, 106, 12938. 11 S. L. Bernasek and G. A. Somorjai, Surf. Sci., 1975, 48, 204. 12 S. G. Sun, A. C. Chen, T. S. Huang, J. B. Li and Z. W. Tian, J. Electroanal. Chem., 1992, 340, 213.

35. More importantly, on high-index planes, there exist short-range steric sites (such as ‘‘chair’’ sites) that are considered as active sites and consist of the combination of several (typical 5–6) step and terrace atoms.13,14 13 R. A. Van Santen, Acc. Chem. Res., 2009, 42, 57. 14 N. Tian, Z. Y. Zhou and S. G. Sun, J. Phys. Chem. C, 2008, 112, 19801. Due to synergistic effect between step and terrace atoms, steric sites usually serve as catalytically active sites. Besides, open-structure surfaces also play a very important role in the charging/discharging process of lithium ion batteries. They can provide parallel channels, where Li+ ions are able to intercalate through the surface with the least resistance compared to other crystal plane orientations.15 This favors fast ion transfer between surface and interior. 15 G. Z. Wei, X. Lu, F. S. Ke, L. Huang, J. T. Li, Z. X. Wang, Z. Y. Zhou and S. G. Sun, Adv. Mater., 2010, 22, 4364.

36. Normally, nanocrystals with low surface energy such as those formed under normal conditions usually have low catalytic activities. Those with high surface energies are known to possess enhanced catalytic properties. The goal here is to create nanocrystal catalysts which have high surface energy facets. Unfortunately, this presents a big challenging. When a crystal grows, different facets grow with different rates. High-energy facets typically have higher growth rates than low-energy facets. Overall, the final crystal shape is dominated by the slow-growth facets that have low surface energy.16 16 H. E. Buckley, Crystal Growth, Wiley, New York, 1951.

37. Remarkably, substantial progress has been made in overcoming the obstacle to form nanocrystals with high-energy facets in recent years.30–32 30 N. Tian, Z. Y. Zhou, S. G. Sun, Y. Ding and Z. L. Wang, Science, 2007, 316, 732. 31 H. G. Yang, C. H. Sun, S. Z. Qiao, J. Zou, G. Liu, S. C. Smith, H. M. Cheng and G. Q. Lu, Nature, 2008, 453, 638. 32 Z. Y. Jiang, Q. Kuang, Z. X. Xie and L. S. Zheng, Adv. Funct. Mater., 2010, 20, 3634.

38. Although there are several excellent reviews about shape controlled synthesis of metal nanocrystals, they mainly describe nanocrystals with low-energy facets.28,33,34 28 Z. M. Peng and H. Yang, Nano Today, 2009, 4, 143. 33 A. R. Tao, S. Habas and P. D. Yang, Small, 2008, 4, 310. 34 Y. Xia, Y. J. Xiong, B. Lim and S. E. Skrabalak, Angew. Chem., Int. Ed., 2009, 48, 60. In this review, after a brief introduction of the relationship between surface structure and crystal shapes, we focus on the recent progress made in shape-controlled synthesis of metal nanocrystals with high-energy facets and open surface structure, including high-index facets and {110} facets, especially electrochemically shape-controlled synthesis of Pt-group metal nanocrystals. Z.-Y. Zhou, N. Tian, J.-T. Li, I. Broadwell and S.-G. Sun, Nanomaterials of high surface energy with exceptional properties in catalysis and energy storage, Chem. Soc. Rev., DOI: 10.1039/c0cs00176g

39. Engineering the shapes of semiconducting functional materials to desirable morphologies has long been actively pursued. This is because many applications such as heterogeneous catalysis, gas sensing and ion detecting, molecule adsorption, energy conversion and storage are very sensitive to surface atomic structures, which can be finely tailored by morphology control.

40. From the intensive studies on morphology-controlled materials in the past decades, significant advancements in this area have been achieved.1–29 1 S. E. Habas, H. Lee, V. Radmilovic, G. A. Somorjai and P. Yang, Nat. Mater., 2007, 6, 692. 2 C. K. Tsung, J. N. Kuhn, W. Y. Huang, C. Aliaga, L. I. Hung, G. A. Somorjai and P. D. Yang, J. Am. Chem. Soc., 2009, 131, 5816. 3 A. Tao, P. Sinsermsuksakul and P. D. Yang, Angew. Chem., Int. Ed., 2006, 45, 4597. 4 A. I. Hochbaum and P. D. Yang, Chem. Rev., 2010, 110, 527. 5 Y. Xia, Y. J. Xiong, B. Lim and S. E. Skrabalak, Angew. Chem., Int. Ed., 2008, 48, 60. 6 B. Wiley, Y. G. Sun, J. Y. Chen, H. Cang, Z. Y. Li, X. D. Li and Y. N. Xia, MRS Bull., 2011, 30, 356. 7 B. Lim, H. Kobayashi, T. Yu, J. G. Wang, M. J. Kim, Z. Y. Li, M. Rycenga and Y. Xia, J. Am. Chem. Soc., 2010, 132, 2506. 8 Y. J. Xiong and Y. N. Xia, Adv. Mater., 2007, 19, 3385. 9 B. Wiley, Y. G. Sun, B. Mayers and Y. N. Xia, Chem.–Eur. J., 2005, 11, 454.

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43. Crystal facet engineering of semiconductor photocatalysts: motivations, advances and unique properties G. Liu, J. C. Yu, G. Q. Luc and H.-M. Cheng. Chem. Comm, DOI: 10.1039/c1cc10665a

44. 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.

45. 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.

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

47. 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.

48. 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.”

49. 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.

50. 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.