ࡱ>  `bjbj ccXNN%%%%8]4l%($!(III}" /(1(1(1(1(1(1(v),x1(}}1(II4F(II/(/(j]#&'_%'2(,\(0('2,,d''N :   An Introduction to Theoretical Chemistry, Second Edition Jack Simons* Chemistry Department University of Utah Salt Lake City, Utah  * Henry Eyring Scientist and Professor of Chemistry Useful websites for further information:  HYPERLINK "http://simons.hec.utah.edu" http://simons.hec.utah.edu Jacks homepage  HYPERLINK "http://simons.hec.utah.edu/TheoryPage" http://simons.hec.utah.edu/TheoryPage Jacks website on theoretical chemistry. Second Edition Introductory Remarks and Table of Contents I am very grateful to Cambridge University Press for agreeing to allow the copyrights on this text to be returned to me so that I could create a Second Edition and make this available at not cost in this online version. Please feel free to reproduce the files constituting this text, but I ask that you not sell any of this material to others; I want it to remain free to everyone. In making the additions and changes needed to prepare this Second Edition, I corrected errors I found in the First Edition and I enhanced the level of presentation in several Chapters where readers of the First Edition had told me such enhancements were needed. However, I tried to keep the overall level of the text appropriate to senior undergraduate or beginning graduate students in good U. S. universities. I apologize for the quality of the presentation made in this Edition; I did not have available the tools that Cambridge University Press had to assure that all the text, figures, and equations appeared in wonderful format. Moreover, I removed the equation numbers to make it easier for me to make additional corrections and additions. I did the best I could, so I hope the readers will be OK with my efforts. Introductory Remarks What is theoretical chemistry? Lets begin by discussing what the discipline of theoretical chemistry is about. I think most students of chemistry think that theory deals with using computers to model or simulate molecular behaviors. This is true, but it is only part of what theory does. Theory indeed contains under its broad umbrella the field of computational simulations, and it is such applications of theory that have gained much recent attention especially as powerful computers and user-friendly software packages have become widely available. Today, every issue of the Journal of Physical Chemistry, the Journal of the American Chemical Society, and the Journal of Chemical Physics contains numerous examples of such theoretical studies. However, the discipline also involves analytical theory, which deals with how the fundamental equations used to perform the simulations are derived from the Schrdinger equation or from classical mechanics. The discipline also has to do with obtaining the equations that relate laboratory data (e.g., spectra, heat capacities, reaction cross-sections, phase diagrams, conductivity) to molecular properties (e.g., geometries, bond energies, activation energies, energy levels, intermolecular potentials). This analytical side of theory is also where the equations of statistical mechanics that relate macroscopic properties of matter to the microscopic properties of the constituent molecules are obtained. So, theory is a diverse field of chemistry that uses physics, mathematics and computers to help us understand molecular behavior, to simulate molecular phenomena, and to predict the properties of new molecules and of new phases of matter. It is common to hear this discipline referred to as theoretical and computational chemistry. This text is focused more on the theory than on the computation. That is, I deal primarily with the basic ideas upon which theoretical chemistry is centered, and I discuss the equations and tools that enter into the three main sub-disciplines of theory- electronic structure, statistical mechanics, and reaction dynamics. I have chosen to emphasize these elements rather than to stress computational applications of theory because there are already many good sources available that deal with computational chemistry. Now, let me address the issue of who does theory? It is common for chemists whose primary research activities involve laboratory work to also use theoretical concepts, equations, simulations and methods to assist in interpreting their data. Sometimes, these researchers also come up with new concepts or new models in terms of which to understand their laboratory findings. These experimental chemists are using theory in the former case and doing new theory in the latter. Many of my experimental chemistry colleagues have evolved into using theory in this manner. However, for several decades now there have also been chemists who do not carry out laboratory experiments but whose research focus lies in developing new theory (new analytical equations, new computational tools, new concepts) and applying theory to understanding chemical processes as a full-time endeavor. These people are what we call theoretical chemists. I am proud to say that I a member of this community of theorists, and that I believe this discipline offers a very powerful background for understanding essentially all other areas of chemistry. Even though people like me do not perform laboratory experiments, it is essential that we understand how experiments are done and what elements of molecular behavior they probe. It is for this reason that I include in this text significant discussion of experimental methods as they relate to the theory upon which I focus. Where does one learn about theoretical chemistry? Most chemistry students in colleges and universities take classes in introductory chemistry, organic, analytical, inorganic, physical, and bio- chemistry. It is extremely rare for students to encounter a class that has theoretical chemistry in its title. This book is intended to illustrate to students that the subject of theoretical chemistry pervades most if not all of the other classes she/he takes in an undergraduate or graduate chemistry curriculum. It is also intended to offer students a modern introduction to the field of theoretical chemistry and to illustrate how it has evolved into a discipline of its own and now stands shoulder-to-shoulder with the traditional experimental sub-disciplines of chemical science. How to use this book I have tried to write this book so it could be used in any of several ways: As a text book that could be used to learn the quantum mechanics and many of the spectroscopy components of a typical junior-or senior-level undergraduate physical chemistry class. This would involve covering Chapters 1-4 as well as Chapter 5, the latter of which offers a brief overview of how theoretical chemistry fits into the research areas of chemistry. It would also be wise to solve many of the problems that I offer in pursuing such an avenue of study. Certainly, any student who has not yet taken an undergraduate class in physical chemistry should follow this route. As a first-year graduate-level text in which selected topics in the areas of introductory quantum chemistry, spectroscopy, statistical mechanics, and the theory of reaction dynamics are surveyed. This would involve covering Chapters 6-8 and solving many of the problems. Although the material of Chapters 1-4 should have been learned by such students in an undergraduate physical chemistry class, it would be wise to read this material to refresh ones memory. It is likely that full-semester classes in statistical mechanics and in reaction dynamics will require more material than offered in Chapters 7 and 8, but these Chapters should suffice for briefer classes and for gaining an introduction to these fields. As an introductory survey source for experimental chemists interested in learning about the central concepts and many of the most common tools of theoretical chemistry. To pursue this avenue, the reader should focus on Chapters 6-8 because the material of Chapters 1-5 covers what such readers probably already know. Because of the flexibility in how this text can be used, some duplication of material occurs. However, it has been my experience that students benefit from encountering subjects more than one time, especially if each subsequent encounter is at a deeper level or makes connections with different applications. I believe this is the case for subjects that are covered in more than one place in this text. I have also offered many exercises (small problems) and problems to be solved by the reader as well as detailed solutions. Most of these problems deal with topics contained in Chapters 1-4 because it is these subjects that are likely to be studied in an undergraduate classroom setting where homework assignments are common. Chapters 6-8 are designed to give the reader an introduction to electronic structure theory, statistical mechanics, and reaction dynamics at the graduate and beginning-research level. In such settings, it is my experience that individual instructors prefer to construct their own problems, so I offer fewer exercises and problems associated with these Chapters. Most, if not all, of the problems presented here require many steps to solve, so the reader is encouraged not to despair when attempting them; they may be difficult, but they teach valuable lessons. Other sources of information Before launching into the subject of theoretical chemistry, allow me to mention other sources that can be used to obtain information at a somewhat more advanced level than is presented in this text. Keep in mind that this is a text intended to offer an introduction to the field of theoretical chemistry, and is directed primarily at advanced undergraduate- and beginning graduate- level readerships. It is my hope that such readers will, from time to time, want to learn more about certain topics that are especially appealing to them. For this purpose, I suggest two sources that I have been instrumental in developing. First, a web site that I created can be accessed at  HYPERLINK "http://simons.hec.utah.edu/TheoryPage" http://simons.hec.utah.edu/TheoryPage. This site provides a wealth of information including 1. web links to home pages of a multitude of practicing theoretical chemists who specialize in many of the topics discussed in this text; 2. numerous education-site web links that allow students ranging from fresh-persons to advanced graduate students to seek out a variety of information; 3. textual information much of which covers at a deeper level those subjects discussed in this text at an introductory level. Another major source of information at a more advanced level is my textbook Quantum Mechanics in Chemistry (QMIC) written with Dr. Jeff Nichols (Past Director of the High Performance Computing Group at the Pacific Northwest National Lab and now Director of Mathematics and Computational Science at Oak Ridge National Lab). The full content of that book can be accessed in .pdf file format through the  HYPERLINK "http://simons.hec.utah.edu/TheoryPage" TheoryPage web link mentioned above. In several locations within the present introductory text, I specifically refer the reader either to my  HYPERLINK "http://simons.hec.utah.edu/TheoryPage" TheoryPage or QMIC textbook, but I urge you to also use these two sources whenever you want a more in-depth treatment of a subject. To the readers who want to access up-to-date research-level treatments of many of the topics we introduce in this text, I suggest several recent monographs to which I refer throughout this text: Molecular Electronic Structure Theory, T. Helgaker, P. Jrgensen, and J. Olsen, J. Wiley, New York, N.Y. (2000), and Modern Electronic Structure Theory, D. R. Yarkony, Ed., World Scientific Publishing, Singapore (1999) Theory of Chemical Reaction Dynamics, M. Baer, Ed., Vols. 1-4; CRC Press, Boca Raton, Fla. (1985) Essentials of Computational Chemistry, C. J. Cramer, Wiley, Chichester (2002). An Introduction to Computational Chemistry, F. Jensen, John Wiley, New York (1998) Molecular Modeling, 2nd ed., A. R. Leach, Prentice Hall, Englewood Cliffs (2001). Molecular Reaction Dynamics and Chemical Reactivity, R. D. Levine and R. B. Bernstein, Oxford University Press, New York (1997) Computer Simulations of Liquids, M. P. Allen and D. J. Tildesley, Oxford U. Press, New York (1997), as well as a few longer-standing texts in areas covered in this work: Statistical Mechanics, D. A. McQuarrie, Harper and Row, New York (1977) Introduction to Modern Statistical Mechanics, D. Chandler, Oxford U. Press, New York (1987) Quantum Chemistry, H. Eyring, J. Walter, and G. E. Kimball, John Wiley, New York (1944) Introduction to Quantum Mechanics, L. Pauling and E. B. Wilson, Dover, New York (1963), Molecular Quantum Mechanics, 3rd Ed., P. W. Atkins and R. S. Friedman, Oxford U. Press, New York (1997). Modern Quantum Chemistry, A. Szabo and N. S. Ostlund, McGraw-Hill, New York (1989). R. N. Zare, Angular Momentum, John Wiley, New York (1988). Because the science of theoretical chemistry makes much use of high-speed computers, it is essential that we appreciate to what extent the computer revolution has impacted this field. Primarily, the advent of modern computers has revolutionized the range of problems to which theoretical chemistry can be applied. Before this revolution, the classical Newtonian or quantum Schrdinger equations in terms of which theory expresses the behavior of atoms and molecules simply could not be solved for any but the simplest species, and then often only by making rather crude approximations. However, present-day computers, which routinely perform 109 operations per second, have 109 bytes of memory and 50 times this much hard disk storage, have made it possible to solve these equations for large collections of molecules and for molecules containing hundreds of atoms and electrons. Moreover, the vast improvement in computing power has inspired many scientists to develop better (more accurate and more efficient) approximations to use in solving these equations. Unfortunately, the undergraduate and beginning graduate- level educations provided to most chemistry majors no longer requires students to learn how to write computer code to embody such new theories. I strongly urge any student interested in pursuing theoretical chemistry to take a class in computer programming or find some other way to learn the basics of this field. Because this text is intended for both an undergraduate and beginning graduate audience and is designed to offer an introduction to the field of theoretical chemistry, it does not devote much time to describing the computer implementation of this subject. Nevertheless, I will attempt to introduce some of the more basic aspects of the computational aspects of theory especially when doing so will help the reader understand the basic principles. In addition, the  HYPERLINK "http://simons.hec.utah.edu/TheoryPage" TheoryPage web site contains a large number of links to scientists and to commercial software providers that can give the reader more detail about the computational aspects of theoretical chemistry. Lets now begin the journey that I hope will give the reader a basic understanding of what theoretical chemistry is and how it fits into the amazing broad discipline of modern chemistry. I hope you learn a lot and do so in a way that is enjoyable to you. Table of Contents Part 1. Background Material HYPERLINK "http://simons.hec.utah.edu/ITCSecondEdition/chapter1.pdf"Chapter 1. The Basics of Quantum Mechanics page 1 1.1 Why Quantum Mechanics is Necessary for Describing Molecular Properties 1.2 The Schrdinger Equation and Its Components 1.2.1 Operators 1.2.2 Wave Functions 1.2.3 The Schrdinger Equation 1.3 Your first application of quantum mechanics- motion of a particle in one dimension. 1.3.1 Classical Probability Density 1.3.2 Quantum Treatment 1.3.3 Energies and Wave functions 1.3.4 Probability Densities 1.3.5 Classical and Quantum Probability Densities 1.3.6 Time Propagation of Wave functions 1.4 Free Particle Motions in More Dimensions 1.4.1 The Schrdinger Equation 1.4.2 Boundary Conditions 1.4.3 Energies and Wave functions for Bound States 1.4.4 Quantized Action Can Also be Used to Derive Energy Levels 1.4.5 Action Can Also be Used to Generate Wave Functions 1.5 Chapter Summary HYPERLINK "http://simons.hec.utah.edu/ITCSecondEdition/chapter2.pdf"Chapter 2. Model Problems That Form Important Starting Points page 95 2.1 Free Electron Model of Polyenes 2.2 Bands of Orbitals in Solids 2.3 Densities of States in 1, 2, and 3 dimensions. 2.4 The Most Elementary Model of Orbital Energy Splittings: Hckel or Tight-Binding Theory 2.5 Hydrogenic Orbitals 2.5.1 The F equation 2.5.2 The Q equation 2.5.3 The R equation 2.6 Electron Tunneling 2.7 Angular Momentum 2.7.1 Orbital angular momentum 2.7.2 Properties of general angular momenta 2.7.3 Summary 2.7.4 Coupling of angular momenta 2.8 Rotations of Molecules 2.8.1 Rotational Motion For Rigid Diatomic and Linear Polyatomic Molecules 2.8.2 Rotational Motions of Rigid Non-Linear Molecules 2.9 Vibrations of Molecules 2.10 Chapter Summary HYPERLINK "http://simons.hec.utah.edu/ITCSecondEdition/chapter3.pdf"Chapter 3. Characteristics of Energy Surfaces page 201 3.1. Strategies for Geometry Optimization and Finding Transition States 3.1.1 Finding Local Minima 3.1.2 Finding Transition States 3.1.3 Energy Surface Intersections 3.2. Normal Modes of Vibration 3.2.1. The Newton Equations of Motion for Vibration 1. The Kinetic and Potential Energy Matrices 2. The Harmonic Vibrational Energies and Normal Mode Eigenvectors 3.2.2. The Use of Symmetry 1. Symmetry Adapted Modes 2. Point Group Symmetry of the Harmonic Potential 3.3 Intrinsic Reaction Paths 3.4 Chapter Summary HYPERLINK "http://simons.hec.utah.edu/ITCSecondEdition/chapter4.pdf"Chapter 4. Some Important Tools of Theory page 229 4.1. Perturbation Theory 4.1.1 An Example Problem 4.1.2 Other Examples 4.2 The Variational Method 4.2.1 An Example Problem 4.2.2 Another Example 4.3. Point Group Symmetry 4.3.1 The C3v Symmetry Group of Ammonia - An Example 4.3.2. Matrices as Group Representations 4.3.3 Characters of Representations 4.3.4. Another Basis and Another Representation 4.3.5 Reducible and Irreducible Representations 4.3.6. More Examples 4.3.7. Projector Operators: Symmetry Adapted Linear Combinations of Atomic Orbitals 4.3.8. Summary 4.3.9 Direct Product Representations 4.3.10 Overview 4.4 Character Tables 4.5 Time Dependent Perturbation Theory 4.6 Chapter Summary Part 2. Three Primary Areas of Theoretical Chemistry HYPERLINK "http://simons.hec.utah.edu/ITCSecondEdition/chapter5.pdf"Chapter 5. An Overview of Theoretical Chemistry page 312 5.1 What is Theoretical Chemistry About? 5.1.1 Molecular Structure- bonding, shapes, electronic structures 5.1.2 Molecular Change- reactions and interactions 1. Changes in Bonding 2. Energy Conservation 3. Conservation of Orbital Symmetry: Woodward-Hoffmann Rules 4. Rates of change 5.1.3. Statistical Mechanics: Treating Large Numbers of Molecules in Close Contact 5.2. Molecular Structure: Theory and Experiment 5.2.1. Experimental Probes of Molecular Shapes 1. Rotational Spectroscopy 2. Vibrational Spectroscopy 3. X-Ray Crystallography 4. NMR Spectroscopy 5.2.2. Theoretical Simulation of Structures 5.3. Chemical Change 5.3.1. Experimental Probes of Chemical Change 5.3.2. Theoretical Simulation of Chemical Change 5.4 Chapter Summary HYPERLINK "http://simons.hec.utah.edu/ITCSecondEdition/chapter6.pdf"Chapter 6. Electronic Structures page 372 6.1 Theoretical Treatment of Electronic Structure: Atomic and Molecular Orbital Theory 6.1.1 Orbitals The Hartree Description The LCAO-Expansion AO Basis Sets STOs and GTOs The Fundamental Core and Valence Basis Polarization Functions Diffuse Functions The Hartree-Fock Approximation Koopmans Theorem Orbital Energies and the Total Energy 5. Molecular Orbitals a. Shapes, Sizes, and Energies of Orbitals b. Bonding, Anti-bonding, Non-bonding, and Rydberg Orbitals 6.1.2 Deficiencies in the Single Determinant Model Electron Correlation Essential Configuration Interaction Various Approaches to Electron Correlation The CI Method Perturbation Theory The Coupled-Cluster Method The Density Functional Method Energy Difference Methods The Slater-Condon Rules Atomic Units 6.1.3 Molecules Embedded in Condensed Media 6.1.4 High-End Methods for Treating Electron Correlation 6.2. Experimental Probes of Electronic Structure 6.2.1 Visible and Ultraviolet Spectroscopy 1. The Electronic Transition Dipole and Use of Point Group Symmetry 2. The Franck-Condon Factors 3. Time Correlation Function Expressions for Transition Rates 4. Line Broadening Mechanisms 6.2.2 Photoelectron Spectroscopy 6.2.3 Probing Continuum Orbitals 6.3 Chapter Summary HYPERLINK "http://simons.hec.utah.edu/ITCSecondEdition/chapter7.pdf"Chapter 7. Statistical Mechanics page 491 7.1. Collections of Molecules at or Near Equilibrium 7.1.1. The Distribution of Energy Among Levels 1. Basis of the Boltzmann Population Formula 2. Equal a priori Probability Assumption 3. The Thermodynamic Limit 4. Fluctuations 7.1.2. Partition Functions and Thermodynamic Properties 1. System Partition Functions 2. Individual-Molecule Partition Functions 7.1.3. Equilibrium Constants in Terms of Partition Functions 7. 2 Monte Carlo Evaluation of Properties 7.2.1 Metropolis Monte Carlo 7.2.2 Umbrella Sampling 7.3 Molecular Dynamics Simulations 7.3.1 Trajectory Propagation 7.3.2 Force Fields 7.3.3 Coarse Graining 7.4 Time Correlation Functions 7.5 Some Important Chemical Applications of Statistical Mechanics 7.5.1 Gas-Molecule Thermodynamics 7.5.2 Einstein and Debye Models of Solids 7.5.3 Lattice Theories of Surfaces and Liquids 7.5.4 Virial Corrections to Ideal-Gas Behavior 7.6 Chapter Summary HYPERLINK "http://simons.hec.utah.edu/ITCSecondEdition/chapter8.pdf"Chapter 8. Chemical Dynamics page 585 8.1 Theoretical Treatment of Chemical Change and Dynamics 8.1.1 Transition State Theory 8.1.2 Variational Transition State Theory 8.1.3 Reaction Path HamiltonianTheory 8.1.4 Classical Dynamics Simulation of Rates 8.1.5 RRKM Theory 8.1.6 Correlation Function Expressions for Rates 8.1.7 Wave Packet Propagation 8.1.8 Surface Hopping Dynamics 8.1.9 Landau-Zener Surface Jumps 8.2 Experimental Probes of Reaction Dynamics 8.2.1 Spectroscopic Methods 8.2.2 Beam Methods 8.2.3 Other Methods 8.3 Chapter Summary  HYPERLINK "http://simons.hec.utah.edu/ITCSecondEdition/Problems.pdf" Problems  HYPERLINK "http://simons.hec.utah.edu/ITCSecondEdition/Solutions.pdf" Solutions PAGE i PAGE xv +9:G   * + , = > q r s Կ}mg]VLVh7nh5CJ h5CJh)h5CJ hCJjjRh-WhCJUh-WhCJh-Wh0JCJjQh-WhCJUh-Wh5CJjh-Wh5CJU h5h)h5B*phjhUhh5B*CJ$phh3hB*phhB*phh;GlB*ph:G\o=    dh`gddhgd $dha$gddhgd $dh@&a$gd $dha$gddhgd dh@&gd   F,b,c,..//9/:/;/`/a/111122223 3 3333ɿ䯿䨿䎙}rih:h0Jj4ThUh_h6hrh0JjwShUjhU h:h h56h7nh5h7nh6h7nh56 h7nh h3hh3h5 h5hh)hB*CJphh3h5CJ' /#%9':'(D, hdh@&`hgd & Fdh@&gd dh@&gd dh@&`gd dh`gddhgddhgdgdD,F,c,/"0091I4 555J666@77%8&8l8m889j99+: dh^gddhgd dh`gd dh@&gd3333333 515555 6J6o6666777=7?7@7s777n88889#9j999999+:E:::?=A=_=`=&B'BZB[B\BfBgB%D&D@DAD]D^DD߻ߴߨjh5U h5 h5CJ h5CJ$jUhUh:h6 hH* h6 h:hhh:h0JjhUjThU<+::::>$C%C%D&D8D\D]DD'EWEgE|EEEF/FQFmFFFFG dh`gddhgd dh^gdDDDDDD&E'EGG8H9H:HCHDHHxIyIII%K&KjKkKlKuKvKKMMMMMMM(NNNNN1OOOO-P.PTPӸӸרטא}xx h\ h%hh%hCJEH\h%h\jYh3*6h5Uj1Xh3*6h5Uh3hOJQJjNWh3*6h5Uh h5h5zh0J5jh5UjkVh3*6h5U.G1GeGGGGGHHHH>IVInIIIIIII%J3JUJqJJJK$K%Kdhgd%KKK L+LNLmLLLM+MEMwMMMM(NANZNoNNNNNO dh1$7$8$H$gdgd dh@&gddhgdO1OUOOOOP.PTPdPyPPPssnnngd $ \ dh1$7$8$H$gd $ \ dh1$7$8$H$gd v$ \ dh1$7$8$H$gd v$ \ dh1$7$8$H$gd *$ \ dh1$7$8$H$gd TPcPdPPPPP1Q2Q3QLwV) ẗ́80t$m6mdՍ.۱Þks 41'HI8bBs\m#ݽq?vTV$7c(3"Xɝ{x$̨Ȇ&e2LΒcѸm \]4:Ƿ%$u9۠|ςwt"yPi9{AӸU&/$#^ИLZ^ x#oe\'撝1:9xG-NEѤ0*!TdaD:؏!M%D*˅{XG!q:aqIO(1'B`4 \5hft'Ki"ښv[kcc]VE=y Udnɽo*?^f#_hHMl=U,qXe\t?2_$9#-.n?)b=ǭk>&gp"Iy(՘ 5JZ[][ȗ;cI0?^krJ3m/md-t{=Rk0m~HGJHWi W$Ү_gC{kMPM7L Np&WD g4d[:4FaPs6sk}/Y3(<,-:h<1,P6<q e pkgs hOIPSL>kxy_ d-%uo195MB !tCykN.#c!(bԉ~=̾7W0#k-ui>獢"I'gًEPźngZWpl_b }Z~,9ˊ'&7C IV܁}斆|]zFGޅ54D5ǏfvYbuϩw15864;mmk-g6N"^jt'MWNIx07jcOX2$ā,-Z#՗K vOo\%%ӐYcl .< } ~r]8PD~t;VUX 52%&kD}7|5e1p2#kۆ~]6ZCH0)Wn]vZLj{Kx {cB^ND8[+yl{}B׶zo%TSAX÷ۡ5^sSjpVFol{b뾩T̮շ0C#߽hVXy/3? דPVk Il_qC>EYsV"ƑMn?7DxϬTmbA66 mޕc66FGhTsA6wn^g@4vǻwWu:V>/i,S؁N>+LïȩA;_r c;l9?IڇI sI{=_"(k]p ?oE^tbIwG= ZZCIyz~$m}u`t:f{HㆴGP/Y&VMF;s׵TݔZ-g;s{K}M='v>;}m. 5 g+G'm-svp]EgpKR] gO>܃Vi;$A9]jzck}qp'ѿ7/?^^M6 #.ֺE%Āv?o殛FLDzOja浢Oak}nlZ3G wa}c;Hݓ7gFR7v{GWusy/uV0O[S+f27pok@]U:U`k\ݾ$4} ۶! `YMEqV?}K1)ډ۹w5;ecCmsN;V XmQmw~[GYPc5ֲlvQuFV CǻSR:S׃^q=KKv׷Sޒu?΂^Ako=$=Ow8BIM'File written by Adobe Photoshop 4.0Adobed            "?   3!1AQa"q2B#$Rb34rC%Scs5&DTdE£t6UeuF'Vfv7GWgw5!1AQaq"2B#R3$brCScs4%&5DTdEU6teuFVfv'7GWgw ?T%>L bI%)^)*8- v:4CvnGР[`{TiښeJ {jjgLj蓝%r rޖ2cJg8t$N!6J5B0{'}:%j[OM䊟Q6 UrRyPG)| *^n ?5$JS_ eADv]P]*StؠlUZr:b^eJ|/T.NQr) 6%«v4v۸ FHY<*MPw#TDJiKuEk2SnjQDJB!ꚧI1#B<Х %`?PdLKJ]uC6pSTM#!KQ}bQ ˫#B$hci aP(}(`D vAK ]>j~W73 CۺxT^XwzYph!ka}e{[:uE2u>{uUvHA ^t ?\y~e=tual?iUcw1km$N (H);%$J}oU?UI(Q@x aJD`'q Q8:89$[37SnڿWv~nD=^ߎ Y/?#6[ˉCz|;O~Ҙ 9 1ٺ ]kO.LT5'UtF5=]4??#$b4Ӄ' zx-%pOܺ]U:H!y24OPMoD#: m.4``!.PV[oQO\1?jg[St_| P:Y{[{$Rqv剕?%0Bc$$dΩ nq.<*1DByI> !J^ Q!SLUla1BJc& 'TMi3->U`"4Ju +Uu*])$rNwOAm^RQ \>QkA;,52$TTaХKGbSRp(!{^8y((dJe"SʋZ;tԵ/];j5Q"s27tO:=AcZ)=r[J'DwBK$hGd[!v':"=KAM&yH' )m )\ێiY$ɰwʮ=ܔRCQvkT8DDIJb$j!8S{$1I@%~*.\Snv]F &AIL=ƽ GekppyEJatB)$V\`e!kżAM t?Y$N/=BJQ;hM1PAjwr]Th3ܤL rAI{ Joi [|䤥7LВ!3:c҂qDcE ))opBzDƩzw8`<0J۟86m#`\OHEO狏~@EaL0Oi&HJPU0g;CaH4T*nHZvE&TG&TZ@hT~ )9n)j"R<%ar7iQ6tDsAV+VdZOP+W[k@k$:xYӤUʺ$W1Ȫ)xXs*}u2 F1M"O 3^5tIJVYo))cP۪$xSi4Rxi owHt>J>%,ɞj@[⒐lŠ'afY$$1${l'uyAѡNZ&RS6ҋ,ox sd$ґlv!4L8BO6) )h5HcRVw u>h2kIqU۷h*瘣t|7a$Ğ8]X#6(k`Wv-FM ^kLHjKKIwbWcusJ?*$! 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