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[物理化学].(Physical.Chemistry,.8ed).Peter.Atkins,.Julio.de.Paula,.文字版.pdf
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ATKINS’ PHYSICAL CHEMISTRY
ATKINS’ PHYSICAL CHEMISTRY
Eighth Edition
Peter Atkins
Professor of Chemistry,
University of Oxford,
and Fellow of Lincoln College, Oxford
Julio de Paula
Professor and Dean of the College of Arts and Sciences
Lewis and Clark College,
Portland, Oregon W. H. Freeman and Company
Library of Congress Control Number: 座机电话号码91
Physical Chemistry, Eighth Edition
? 2006 by Peter Atkins and Julio de Paula
All rights reserved
座机电话号码87594
Published in Great Britain by Oxford University Press
This edition has been authorized by Oxford University Press for sale in the
United States and Canada only and not for export therefrom.
First printing
W. H. Freeman and Company
41 Madison Avenue
New York, NY 10010
We have taken the opportunity to refresh both the content and presentation of this
text while―as for all its editions―keeping it ?exible to use, accessible to students,
broad in scope, and authoritative. The bulk of textbooks is a perennial concern: we
have sought to tighten the presentation in this edition. However, it should always be
borne in mind that much of the bulk arises from the numerous pedagogical features
that we include
such as Worked examples and the Data section , not necessarily from
density of information. The most striking change in presentation is the use of colour. We have made every
systematically
pedagogically,
gratuitously,
medium for making the text more attractive but using it to convey concepts and data
more clearly. The text is still divided into three parts, but material has been moved
between chapters and the chapters have been reorganized. We have responded to the
shift in emphasis away from classical thermodynamics by combining several chapters
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淘豆网网友近日为您收集整理了关于Physics - Quantum Mechanics Textbook For Chemistry的文档，希望对您的工作和学习有所帮助。以下是文档介绍：Physics - Quantum Mechanics Textbook For Chemistry Words to the reader about how to use this textbookI. What This Book Does and Does Not ContainThis text is intended for use by beginning graduate students and advanced upperdivision undergraduate students in all areas of chemistry.It provides:(i) An introduction to the fundamentals of quantum mechanics as they apply to chemistry,(ii) Material that provides brief introductions to the subjects of molecular spectroscopy andchemical dynamics,(iii) An(来源：淘豆网[/p-5722883.html]) introduction putational chemistry applied to the treatment of electronicstructures of atoms, molecules, radicals, and ions,(iv) A large number of exercises, problems, and detailed solutions.It does not provide much historical perspective on the development of quantummechanics. Subjects such as the photoelectric effect, black-body radiation, the dual natureof electrons and photons, and the Davisson and Germer experiments are not evendiscussed.To pro(来源：淘豆网[/p-5722883.html])vide a text that students can use to gain introductory level knowledge ofquantum mechanics as applied to chemistry problems, such a non-historical approach hadto be followed. This text immediately exposes the reader to the machinery of quantummechanics.Sections 1 and 2 (i.e., Chapters 1-7), together with Appendices A, B, C and E,could constitute a one-semester course for most first-year Ph. D. programs in the U. S. A.Section 3 (Chapters 8-12) and se(来源：淘豆网[/p-5722883.html])lected material from other appendices or selections fromSection 6 would be appropriate for a second-quarter or second-semester course. Chapters13- 15 of Sections 4 and 5 would be of use for providing a link to a one-quarter or one-semester class covering molecular spectroscopy. Chapter 16 of Section 5 provides a briefintroduction to chemical dynamics that could be used at the beginning of a class on thissubject.There are many quantum chemistry and q(来源：淘豆网[/p-5722883.html])uantum mechanics textbooks that covermaterial similar to that contained in Sections 1 and 2; in fact, our treatment of this materialis generally briefer and less detailed than one finds in, for example, Quantum Chemistry,H. Eyring, J. Walter, and G. E. Kimball, J. Wiley and Sons, New York, N.Y. (1947),Quantum Chemistry, D. A. McQuarrie, University Science Books, Mill Valley, Ca.(1983), Molecular Quantum Mechanics, P. W. Atkins, Oxford Univ. Press, O(来源：淘豆网[/p-5722883.html])xford,England (1983), or Quantum Chemistry, I. N. Levine, Prentice Hall, Englewood Cliffs,N. J. (1991), Depending on the backgrounds of the students, our coverage may have to besupplemented in these first two Sections.By covering this introductory material in less detail, we are able, within theconfines of a text that can be used for a one-year or a two-quarter course, to introduce thestudent to the more modern subjects treated in Sections 3, 5, and(来源：淘豆网[/p-5722883.html]) 6. Our coverage ofmodern quantum chemistry methodology is not as detailed as that found in ModernQuantum Chemistry, A. Szabo and N. S. Ostlund, Mc Graw-Hill, New York (1989),which contains little or none of the introductory material of our Sections 1 and 2.bining both introductory and modern up-to-date quantum chemistry materialin a single book designed to serve as a text for one-quarter, one-semester, two-quarter, orone-year classes for first-year(来源：淘豆网[/p-5722883.html]) graduate students, we offer a unique product.It is anticipated that a course dealing with atomic and molecular spectroscopy willfollow the student's mastery of the material covered in Sections 1- 4. For this reason,beyond these introductory sections, this text's emphasis is placed on electronic structureapplications rather than on vibrational and rotational energy levels, which are traditionallycovered in considerable detail in spectroscopy(来源：淘豆网[/p-5722883.html]) courses.In brief summary, this book includes the following material:1. The Section entitled The Basic Tools of Quantum Mechanics treatsthe fundamental postulates of quantum mechanics and several applications to exactlysoluble model problems. These problems include the conventional particle-in-a-box (in oneand more dimensions), rigid-rotor, harmonic oscillator, and one-electron hydrogenicatomic orbitals. The concept of the Born-Oppenheimer separatio(来源：淘豆网[/p-5722883.html])n of electronic andvibration-rotation motions is introduced here. Moreover, the vibrational and rotationalenergies, states, and wavefunctions of diatomic, linear polyatomic and non-linearpolyatomic molecules are discussed here at an introductory level. This section alsointroduces the variational method and perturbation theory as tools that are used to deal withproblems that can not be solved exactly.2. The Section Simple Molecular Orbital Theory dea(来源：淘豆网[/p-5722883.html])ls with atomic andmolecular orbitals in a qualitative manner, including their symmetries, shapes, sizes, andenergies. It introduces bonding, non-bonding, and antibonding orbitals, delocalized,hybrid, and Rydberg orbitals, and introduces Hückel-level models for the calculation ofmolecular orbitals as binations of atomic orbitals (a more extensive treatment ofseveral semi-empirical methods is provided in Appendix F). This section also developsthe Orbital Correlation Diagram concept that plays a central role in using Woodward-Hoffmann rules to predict whether chemical reactions encounter symmetry-imposedbarriers.3. The Electronic Configurations, Term Symbols, and StatesSection treats the spatial, angular momentum, and spin symmetries of the many-electronwavefunctions that are formed as antisymmetrized products of atomic or molecular orbitals.Proper coupling of angular momenta (orbital and spin) is covered here, and atomic andmolecular term symbols are treated. The need to include Configuration Interaction toachieve qualitatively correct descriptions of certain species' electronic structures is treatedhere. The role of the resultant Configuration Correlation Diagrams in the Woodward-Hoffmann theory of chemical reactivity is also developed.4. The Section on Molecular Rotation and Vibration provides anintroduction to how vibrational and rotational energy levels and wavefunctions areexpressed for diatomic, linear polyatomic, and non-linear polyatomic molecules whoseelectronic energies are described by a single potential energy surface. Rotations of &rigid&molecules and harmonic vibrations of uncoupled normal modes constitute the starting pointof such treatments.5. The Time Dependent Processes Section uses time-dependent perturbationtheory, combined with the classical electric and ic fields that arise due to theinteraction of photons with the nuclei and electrons of a molecule, to derive expressions forthe rates of transitions among atomic or molecular electronic, vibrational, and rotationalstates induced by photon absorption or emission. Sources of line broadening and timecorrelation function treatments of absorption lineshapes are briefly introduced. Finally,transitions induced by collisions rather than by ic fields are briefly treated toprovide an introduction to the subject of theoretical chemical dynamics.6. The Section on More Quantitive Aspects of Electronic StructureCalculations introduces many of putational chemistry methods that are usedto quantitatively evaluate molecular orbital and configuration mixing amplitudes. TheHartree-Fock self-consistent field (SCF), configuration interaction (CI),multiconfigurational SCF (MCSCF), many-body and Mller-Plesset perturbation theories,coupled-cluster (CC), and density functional or Xα-like methods are included. Thestrengths and weaknesses of each of these techniques are discussed in some detail. Havingmastered this section, the reader should be familiar with how potential energyhypersurfaces, molecular properties, forces on the individual atomic centers, and responsesto externally applied fields or perturbations are evaluated on high puters.II. How to Use This Book: Other Sources of Information and Building NecessaryBackgroundIn most class room settings, the group of students learning quantum mechanics as itapplies to chemistry have quite diverse backgrounds. In particular, the level of preparationin mathematics is likely to vary considerably from student to student, as will the exposureto symmetry and group theory. This text anized in a manner that allows students toskip material that is already familiar while providing access to most if not all necessarybackground material. This is plished by dividing the material into sections, chaptersand Appendices which fill in the background, provide methodological tools, and provideadditional details.The Appendices covering Point Group Symmetry and Mathematics Review areespecially important to master. Neither of these two Appendices provides a first-principlestreatment of their subject matter. The students are assumed to have fulfilled normalAmerican Chemical Society mathematics requirements for a degree in chemistry, so only areview of the material especially relevant to quantum chemistry is given in the MathematicsReview Appendix. Likewise, the student is assumed to have learned or to besimultaneously learning about symmetry and group theory as applied to chemistry, so thissubject is treated in a review and practical-application manner here. If group theory is to beincluded as an integral part of the class, then this text should be supplemented (e.g., byusing the text Chemical Applications of Group Theory, F. A. Cotton, Interscience, NewYork, N. Y. (1963)).The progression of sections leads the reader from the principles of quantummechanics and several model problems which illustrate these principles and relate tochemical phenomena, through atomic and molecular orbitals, N-electron configurations,states, and term symbols, vibrational and rotational energy levels, photon-inducedtransitions among various levels, and eventually putational techniques for treatingchemical bonding and reactivity.At the end of each Section, a set of Review Exercises and fully worked outanswers are given. Attempting to work these exercises should allow the student todetermine whether he or she needs to pursue additional background building via theAppendices .In addition to the Review Exercises , sets of Exercises and Problems, andtheir solutions, are given at the end of each section.The exercises are brief and highly focused on learning a particular skill. They allow thestudent to practice the mathematical steps and other material introduced in the section. Theproblems are more extensive and require that numerous steps be executed. They illustrateapplication of the material contained in the chapter to chemical phenomena and they helpteach the relevance of this material to experimental chemistry. In many cases, new materialis introduced in the problems, so all readers are encouraged to e actively involved insolving all problems.To further assist the learning process, readers may find it useful to consult othertextbooks or literature references. Several particular texts are mended for additionalreading, further details, or simply an alternative point of view. They include the following(in each case, the abbreviated name used in this text is given following the properreference):1. Quantum Chemistry, H. Eyring, J. Walter, and G. E. Kimball, J. Wileyand Sons, New York, N.Y. (1947)- EWK.2. Quantum Chemistry, D. A. McQuarrie, University Science Books, Mill Valley, Ca.(1983)- McQuarrie.3. Molecular Quantum Mechanics, P. W. Atkins, Oxford Univ. Press, Oxford, England(1983)- Atkins.4. The Fundamental Principles of Quantum Mechanics, E. C. Kemble, McGraw-Hill, NewYork, N.Y. (1937)- Kemble.5. The Theory of Atomic Spectra, E. U. Condon and G. H. Shortley, Cambridge Univ.Press, Cambridge, England (1963)- Condon and Shortley.6. The Principles of Quantum Mechanics, P. A. M. Dirac, Oxford Univ. Press, Oxford,England (1947)- Dirac.7. Molecular Vibrations, E. B. Wilson, J. C. Decius, and P. C. Cross, Dover Pub., NewYork, N. Y. (1955)- WDC.8. Chemical Applications of Group Theory, F. A. Cotton, Interscience, New York, N. Y.(1963)- Cotton.9. Angular Momentum, R. N. Zare, John Wiley and Sons, New York, N. Y. (1988)-Zare.10. Introduction to Quantum Mechanics, L. Pauling and E. B. Wilson, Dover Publications,Inc., New York, N. Y. (1963)- Pauling and Wilson.11. Modern Quantum Chemistry, A. Szabo and N. S. Ostlund, Mc Graw-Hill, New York(1989)- Szabo and Ostlund.12. Quantum Chemistry, I. N. Levine, Prentice Hall, Englewood Cliffs, N. J. (1991)-Levine.13. Energetic Principles of Chemical Reactions, J. Simons, Jones and Bartlett, PortolaValley, Calif. (1983),Section 1 The Basic Tools of Quantum MechanicsChapter 1Quantum Mechanics Describes Matter in Terms of Wavefunctions and Energy Levels.Physical Measurements are Described in Terms of Operators Acting on WavefunctionsI. Operators, Wavefunctions, and the Schrdinger EquationThe trends in chemical and physical properties of the elements described beautifullyin the periodic table and the ability of early spectroscopists to fit atomic line spectra bysimple mathematical formulas and to interpret atomic electronic states in terms of empiricalquantum numbers pelling evidence that some relatively simple frameworkmust exist for understanding the electronic structures of all atoms. The great predictivepower of the concept of atomic valence further suggests that molecular electronic structureshould be understandable in terms of those of the constituent atoms.Much of quantum chemistry attempts to make more quantitative these aspects ofchemists' view of the periodic table and of atomic valence and structure. By starting from'first principles' and treating atomic and molecular states as solutions of a so-calledSchrdinger equation, quantum chemistry seeks to determine what underlies the empiricalquantum numbers, orbitals, the aufbau principle and the concept of valence used byspectroscopists and chemists, in some cases, even prior to the advent of quantummechanics.Quantum mechanics is cast in a language that is not familiar to most students ofchemistry who are examining the subject for the first time. Its mathematical content andhow it relates to experimental measurements both require a great deal of effort to master.With these thoughts in mind, the authors anized this introductory section in amanner that first provides the student with a brief introduction to the two primaryconstructs of quantum mechanics, operators and wavefunctions that obey a Schrdingerequation, then demonstrates the application of these constructs to several chemicallyrelevant model problems, and finally returns to examine in more detail the conceptualstructure of quantum mechanics.By learning the solutions of the Schrdinger equation for a few model systems, thestudent can better appreciate the treatment of the fundamental postulates of quantummechanics as well as their relation to experimental measurement because the wavefunctionsof the known model problems can be used to illustrate.A. OperatorsEach physically measurable quantity has a corresponding operator. The eigenvaluesof the operator tell the values of the corresponding physical property that can be observedIn quantum mechanics, any experimentally measurable physical quantity F (e.g.,energy, dipole moment, orbital angular momentum, spin angular momentum, linearmomentum, ic energy) whose classical mechanical expression can be written in termsof the cartesian positions {qi} and momenta {pi} of the particles prise the systemof interest is assigned a corresponding quantum mechanical operator F. Given F in termsof the {qi} and {pi}, F is formed by replacing pj by -ih/qj and leaving qj untouched.For example, ifF=Σl=1,N (pl2/2ml + 1/2 k(ql-ql0)2 + L(ql-ql0)),thenF=Σl=1,N (- h2/2ml 2/ql2 + 1/2 k(ql-ql0)2 + L(ql-ql0))is the corresponding quantum mechanical operator. Such an operator would occur when,for example, one describes the sum of the ic energies of a collection of particles (theΣl=1,N (pl2/2ml ) term, plus the sum of &Hookes' Law& parabolic potentials (the 1/2 Σl=1,Nk(ql-ql0)2), and (the last term in F) the interactions of the particles with an externallyapplied field whose potential energy varies linearly as the particles move away from theirequilibrium positions {ql0}.The sum of the ponents of angular momenta of a collection of N particles hasF=Σj=1,N (xjpyj - yjpxj),and the corresponding operator isF=-ih Σj=1,N (xj/yj - yj/xj).The ponent of the dipole moment for a collection of N particleshasF=Σj=1,N Zjexj, andF=Σj=1,N Zjexj ,where Zje is the charge on the jth particle.The mapping from F to F is straightforward only in terms of cartesian coordinates.To map a classical function F, given in terms of curvilinear coordinates (even if they areorthogonal), into its quantum operator is not at all straightforward. Interested readers arereferred to Kemble's text on quantum mechanics which deals with this matter in detail. Themapping can always be done in terms of cartesian coordinates after which a transformationof the resulting coordinates and differential operators to a curvilinear system can beperformed. The corresponding transformation of the ic energy operator to sphericalcoordinates is treated in detail in Appendix A. The text by EWK also covers this topic inconsiderable detail.The relationship of these quantum mechanical operators to experimentalmeasurement will be made clear later in this chapter. For now, suffice it to say that theseoperators define equations whose solutions determine the values of the correspondingphysical property that can be observed when a measur only the valuesso determined can be observed. This should suggest the origins of quantum mechanics'prediction that some measurements will produce discrete or quantized values of certainvariables (e.g., energy, angular momentum, etc.).B. WavefunctionsThe eigenfunctions of a quantum mechanical operator depend on the coordinatesupon whi these functions are called wavefunctionsIn addition to operators corresponding to each physically measurable quantity,quantum mechanics describes the state of the system in terms of a wavefunction Ψ that is afunction of the coordinates {qj} and of time t. The function |Ψ(qj,t)|2 = Ψ*Ψ gives theprobability density for observing the coordinates at the values qj at time t. For a many-particle system such as the H2O molecule, the wavefunction depends on many coordinates.For the H2O example, it depends on the x, y, and z (or r,θ, and φ) coordinates of the tenelectrons and the x, y, and z (or r,θ, and φ) coordinates of the oxygen nucleus a a total of thirty-nine coordinates appear in Ψ.In classical mechanics, the coordinates qj and their corresponding momenta pj arefunctions of time. The state of the system is then described by specifying qj(t) and pj(t). Inquantum mechanics, the concept that qj is known as a function of time is replaced by theconcept of the probability density for finding qj at a particular value at a particular time t:|Ψ(qj,t)|2. Knowledge of the corresponding momenta as functions of time is alsorelinquished
again, only knowledge of the probability density forfinding pj with any particular value at a particular time t remains.C. The Schrdinger EquationThis equation is an eigenvalue equation for the energy or H itseigenvalues provide the energy levels of the system1. The Time-Dependent EquationIf the Hamiltonian operator contains the time variable explicitly, one must solve thetime-dependent Schrdinger equationHow to extract from Ψ(qj,t) knowledge about momenta is treated below in Sec. III.A, where the structure of quantum mechanics, the use of operators and wavefunctions tomake predictions and interpretations about experimental measurements, and the origin of'uncertainty relations' such as the well known Heisenberg uncertainty condition dealingwith measurements of coordinates and momenta are also treated.Before moving deeper into understanding what quantum mechanics 'means', it isuseful to learn how the wavefunctions Ψ are found by applying the basic equation ofquantum mechanics, the Schrdinger equation, to a few exactly soluble model problems.Knowing the solutions to these 'easy' yet chemically very relevant models will thenfacilitate learning more of the details about the structure of quantum mechanics becausethese model cases can be used as 'concrete examples'.The Schrdinger equation is a differential equation depending on time and on all ofthe spatial coordinates necessary to describe the system at hand (thirty-nine for the H2Oexample cited above). It is usually writtenH Ψ= i h Ψ/t播放器加载中，请稍候...
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Physics - Quantum Mechanics Textbook For Chemistry Words to the reader about how to use this textbookI. What This Book Does and Does Not ContainThis text is intended for use by beginning graduate students and advanced upperdivision undergraduate students in all areas of chemistry.It provides:(i) An ...
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