CONTENTS Pure rotation spectra 441 Discussion questions 13.4Mo 441 Exercises 13.5 The rotational energy levels 443 Problems 510 135 Rotational transitions 446 deanaoaioalsae 15 Molecular spectroscopy 3:magnetic resonance 513 The vibr ns of diatomic molecules ibration 52 The effect of magnetic fields on electrons and nuclei 513 ction rule 45 15.1 The energies of electrons in magnetic fields 513 455 15.2 The energies of nuckei in magnetic fields 15.3 Magnetic resonance spectroscopy 13.12 Vibration- tation spectra 457 13.13 Vibrational Raman spectra of diatomic molecules 459 Nuclear magnetic resonance 517 15.4 The NMR spectrometer The vibrations of polyatomicr 460 15.5 The chemical shif 3.15 Infrared absorption pectra of polyatomic 460 ion and exchange molecules 532 113.2 Impact on environmental sience:Globa 462 Pulse techniges in NMR 533 13.16 Vibrational Raman spectra ofpolyatomic 15.8Th vector 533 molecules 159c 464 536 stry:Vibrational microscopy 115.1 Impact on medicine:Magnetic resonance imaging 540 15.10 Spin decoupling Symmetry aspe 46 541 15.11 The nuclear Overhaus 9 470 15.13 4% Further information 13.1:Spectrometers 470 Further information 13.2:Selection rules for rotational Electron paramagnetic resonance oscopy 473 15.14 The EPR spectrometer n que 1 The g-va 478 Checklist of kev 14 Molecular spectroscopy 2:electronic transitions 481 deas Further reading Further 15.1:Fourier transfommation of the The characteristics of electronic transitions FID curve 4.1 490 Problems 557 The fates of elec ically excited states 4 492 16 Statistical thermodynamics1:the concepts 114.2 Impact on biochemistry:Fluorescence 494 The states 495 561 Lasers 496 564 H6.1 r.The helix-coil 308 transition in polypeptides 571 Checklist ot kev ideas 505 The intemal eneray and the entropy 573 506 16.3 The internal en 573 Further infomation 14.1:Examplesof practical lasers 16.4 The statistical entropy 575
xxvi CONTENTS Pure rotation spectra 441 13.4 Moments of inertia 441 13.5 The rotational energy levels 443 13.6 Rotational transitions 446 13.7 Rotational Raman spectra 449 13.8 Nuclear statistics and rotational states 450 The vibrations of diatomic molecules 452 13.9 Molecular vibrations 452 13.10 Selection rules 454 13.11 Anharmonicity 455 13.12 Vibration–rotation spectra 457 13.13 Vibrational Raman spectra of diatomic molecules 459 The vibrations of polyatomic molecules 460 13.14 Normal modes 460 13.15 Infrared absorption spectra of polyatomic molecules 461 I13.2 Impact on environmental science: Global warming 462 13.16 Vibrational Raman spectra of polyatomic molecules 464 I13.3 Impact on biochemistry: Vibrational microscopy 466 13.17 Symmetry aspects of molecular vibrations 466 Checklist of key ideas 469 Further reading 470 Further information 13.1: Spectrometers 470 Further information 13.2: Selection rules for rotational and vibrational spectroscopy 473 Discussion questions 476 Exercises 476 Problems 478 14 Molecular spectroscopy 2: electronic transitions 481 The characteristics of electronic transitions 481 14.1 The electronic spectra of diatomic molecules 482 14.2 The electronic spectra of polyatomic molecules 487 I14.1 Impact on biochemistry: Vision 490 The fates of electronically excited states 492 14.3 Fluorescence and phosphorescence 492 I14.2 Impact on biochemistry: Fluorescence microscopy 494 14.4 Dissociation and predissociation 495 Lasers 496 14.5 General principles of laser action 496 14.6 Applications of lasers in chemistry 500 Checklist of key ideas 505 Further reading 506 Further information 14.1: Examples of practical lasers 506 Discussion questions 508 Exercises 509 Problems 510 15 Molecular spectroscopy 3: magnetic resonance 513 The effect of magnetic fields on electrons and nuclei 513 15.1 The energies of electrons in magnetic fields 513 15.2 The energies of nuclei in magnetic fields 515 15.3 Magnetic resonance spectroscopy 516 Nuclear magnetic resonance 517 15.4 The NMR spectrometer 517 15.5 The chemical shift 518 15.6 The fine structure 524 15.7 Conformational conversion and exchange processes 532 Pulse techniqes in NMR 533 15.8 The magnetization vector 533 15.9 Spin relaxation 536 I15.1 Impact on medicine: Magnetic resonance imaging 540 15.10 Spin decoupling 541 15.11 The nuclear Overhauser effect 542 15.12 Two-dimensional NMR 544 15.13 Solid-state NMR 548 Electron paramagnetic resonance 549 15.14 The EPR spectrometer 549 15.15 The g-value 550 15.16 Hyperfine structure 551 I15.2 Impact on biochemistry: Spin probes 553 Checklist of key ideas 554 Further reading 555 Further information 15.1: Fourier transformation of the FID curve 555 Discussion questions 556 Exercises 556 Problems 557 16 Statistical thermodynamics 1: the concepts 560 The distribution of molecular states 561 16.1 Configurations and weights 561 16.2 The molecular partition function 564 I16.1 Impact on biochemistry: The helix–coil transition in polypeptides 571 The internal energy and the entropy 573 16.3 The internal energy 573 16.4 The statistical entropy 575
CONTENTS xxvii The canonical partition function 577 Checklist of key ideas 646 16.5 The canonical ensemble Further reading 16.6 The ther ocdnarmicinformationinthc 57 16.7 Independent molecule 79 647 Discussion questions 648 582 Exercises Problems 649 ation 16.1:The Boltzmann distribution 582 583 Further intormation 16.3:Temperatures below zero 19 Materials 1:macromolecules and aggregates 652 cussion questions Determination of size and shape 652 19.2 Mass spectrometry 6 19.3 Laser light scattering 17 Statistical thermodynamics 2:applications 589 194 868 Fur ental relati 599 664 19.6 Viscosity 665 r par 59 Using statistical thermodynamics 599 Structure and dynamics 667 19.7 can ene The different levels of structure Random coils s ofstat The structure polymers 17.6 Molecular interactions in liquids 606 Residual entropies 19.10 ng polymer 17.7 609 17.8 Equilibrium constants 610 19.11 The structure of nucleic acids 19.12 The stability of proteins and nucleic acids 681 urther reading Self-assembly 681 19.13 Colloids 617 Miclles and biological membrane 618 :Nanofabrication with 690 18 Molecular interactions 620 Checklist of key ideas Electric pro perties of molecules Further reading 91:The Rayleigh ratio 18 Polarizabilities nents 620 624 627 Problems ctions be molecules 629 629 20 Materials2:the solid state 697 185 Repulsive and total interactions 118.1 In act on medicine:Molecular recognition Crystal lattices and drug design 638 0 Latices and unit cell 837 Gases and liquids 640 203 attice planes 708 18.6 Molecular interactions in gases 640 120.1 Impact on biochemistr y:X-ray crystallography 18.7 The liquid- 641 of biological macromolecules 18.8 645 20.4 Neutron and electron diffraction
CONTENTS xxvii Checklist of key ideas 646 Further reading 646 Further information 18.1: The dipole–dipole interaction 646 Further information 18.2: The basic principles of molecular beams 647 Discussion questions 648 Exercises 648 Problems 649 19 Materials 1: macromolecules and aggregates 652 Determination of size and shape 652 19.1 Mean molar masses 653 19.2 Mass spectrometry 655 19.3 Laser light scattering 657 19.4 Ultracentrifugation 660 19.5 Electrophoresis 663 I19.1 Impact on biochemistry: Gel electrophoresis in genomics and proteomics 664 19.6 Viscosity 665 Structure and dynamics 667 19.7 The different levels of structure 667 19.8 Random coils 668 19.9 The structure and stability of synthetic polymers 673 I19.2 Impact on technology: Conducting polymers 674 19.10 The structure of proteins 675 19.11 The structure of nucleic acids 679 19.12 The stability of proteins and nucleic acids 681 Self-assembly 681 19.13 Colloids 682 19.14 Micelles and biological membranes 685 19.15 Surface films 687 I19.3 Impact on nanoscience: Nanofabrication with self-assembled monolayers 690 Checklist of key ideas 690 Further reading 691 Further information 19.1: The Rayleigh ratio 691 Discussion questions 692 Exercises 692 Problems 693 20 Materials 2: the solid state 697 Crystal lattices 697 20.1 Lattices and unit cells 697 20.2 The identification of lattice planes 700 20.3 The investigation of structure 702 I20.1 Impact on biochemistry: X-ray crystallography of biological macromolecules 711 20.4 Neutron and electron diffraction 713 The canonical partition function 577 16.5 The canonical ensemble 577 16.6 The thermodynamic information in the partition function 578 16.7 Independent molecules 579 Checklist of key ideas 581 Further reading 582 Further information 16.1: The Boltzmann distribution 582 Further information 16.2: The Boltzmann formula 583 Further information 16.3: Temperatures below zero 584 Discussion questions 585 Exercises 586 Problems 586 17 Statistical thermodynamics 2: applications 589 Fundamental relations 589 17.1 The thermodynamic functions 589 17.2 The molecular partition function 591 Using statistical thermodynamics 599 17.3 Mean energies 599 17.4 Heat capacities 601 17.5 Equations of state 604 17.6 Molecular interactions in liquids 606 17.7 Residual entropies 609 17.8 Equilibrium constants 610 Checklist of key ideas 615 Further reading 615 Discussion questions 617 Exercises 617 Problems 618 18 Molecular interactions 620 Electric properties of molecules 620 18.1 Electric dipole moments 620 18.2 Polarizabilities 624 18.3 Relative permittivities 627 Interactions between molecules 629 18.4 Interactions between dipoles 629 18.5 Repulsive and total interactions 637 I18.1 Impact on medicine: Molecular recognition and drug design 638 Gases and liquids 640 18.6 Molecular interactions in gases 640 18.7 The liquid–vapour interface 641 18.8 Condensation 645
CONTENTS Crystal structure 715 22 The rates of chemical reactions 791 20.5 Metallic solids 715 20.6 Ionic solids 717 Empirieal chemical kinetice 791 20.7 Molecular solids and covalent networks 720 22.1 Experimental technique 721 22.2 The rates of reactions 多 22.3 Integrated rate law 22.4 20.2lm oscience:Nanowires 738 22.5 20.10 Optical properties 728 Accounting for the rate laws 809 20.11 Magnetic properties 733 s09 20.12 Superconductors 736 22700 action 811 Checklist of key ideas otransition in polypeptides Discussion questions 739 Exercises 740 eckistof k ideas Problems 741 Further 22.1:The RRK model of unimolecular reactions PART 3 Change 745 Discussion questions 21 Molecules in motion 747 Molecular motion in gases 747 23 The kinetics of complex reactions 830 21.1 The kinetic model ofgases 748 121.1 Impact on astrophysics:The Sun asa ball of Chain reactions 830 21.2 ith walls and surfaces 23.1 The rate laws of chain reactions 0 21.3 The rate of effusion 756 23.2 Explosions 21.4 Transport properties ofa perfect gas 757 Polymerization kinetics Molecular motioninliquids 761 21 Hom 218 f electrolyte solutions eous catalysis 839 23.5 Features ofhomogeneous catalysis 769 23.6 Enzymes 840 pumps 770 Photochemistry 845 23.7 Kinetics ofphotophysical and photochemical 772 processe 845 he the 21.10 The vicw 76 123.1 of stratospheric ozone 853 123.2 Impact on biochemistry:Harvesting oflight electrolytes across biological membranes 779 ing plant photosynt 21.11 Diffus 856 The 781 nedicine:Pho mic therap 860 Checklist of key ideas 783 Checklist of key ideas 61 Further reading 783 Further reading 8 Further infoaion 21.1:The transport characteristics of Further intommation 23.1:The Forster theory of resonance gas n questions uestions 78 863 Problems 788 Problems 864
xxviii CONTENTS Crystal structure 715 20.5 Metallic solids 715 20.6 Ionic solids 717 20.7 Molecular solids and covalent networks 720 The properties of solids 721 20.8 Mechanical properties 721 20.9 Electrical properties 723 I20.2 Impact on nanoscience: Nanowires 728 20.10 Optical properties 728 20.11 Magnetic properties 733 20.12 Superconductors 736 Checklist of key ideas 738 Further reading 739 Discussion questions 739 Exercises 740 Problems 741 PART 3 Change 745 21 Molecules in motion 747 Molecular motion in gases 747 21.1 The kinetic model of gases 748 I21.1 Impact on astrophysics: The Sun as a ball of perfect gas 754 21.2 Collision with walls and surfaces 755 21.3 The rate of effusion 756 21.4 Transport properties of a perfect gas 757 Molecular motion in liquids 761 21.5 Experimental results 761 21.6 The conductivities of electrolyte solutions 761 21.7 The mobilities of ions 764 21.8 Conductivities and ion–ion interactions 769 I21.2 Impact on biochemistry: Ion channels and ion pumps 770 Diffusion 772 21.9 The thermodynamic view 772 21.10 The diffusion equation 776 I21.3 Impact on biochemistry: Transport of nonelectrolytes across biological membranes 779 21.11 Diffusion probabilities 780 21.12 The statistical view 781 Checklist of key ideas 783 Further reading 783 Further information 21.1: The transport characteristics of a perfect gas 784 Discussion questions 785 Exercises 786 Problems 788 22 The rates of chemical reactions 791 Empirical chemical kinetics 791 22.1 Experimental techniques 792 22.2 The rates of reactions 794 22.3 Integrated rate laws 798 22.4 Reactions approaching equilibrium 804 22.5 The temperature dependence of reaction rates 807 Accounting for the rate laws 809 22.6 Elementary reactions 809 22.7 Consecutive elementary reactions 811 I22.1 Impact on biochemistry: The kinetics of the helix–coil transition in polypeptides 818 22.8 Unimolecular reactions 820 Checklist of key ideas 823 Further reading 823 Further information 22.1: The RRK model of unimolecular reactions 824 Discussion questions 825 Exercises 825 Problems 826 23 The kinetics of complex reactions 830 Chain reactions 830 23.1 The rate laws of chain reactions 830 23.2 Explosions 833 Polymerization kinetics 835 23.3 Stepwise polymerization 835 23.4 Chain polymerization 836 Homogeneous catalysis 839 23.5 Features of homogeneous catalysis 839 23.6 Enzymes 840 Photochemistry 845 23.7 Kinetics of photophysical and photochemical processes 845 I23.1 Impact on environmental science: The chemistry of stratospheric ozone 853 I23.2 Impact on biochemistry: Harvesting of light during plant photosynthesis 856 23.8 Complex photochemical processes 858 I23.3 Impact on medicine: Photodynamic therapy 860 Checklist of key ideas 861 Further reading 862 Further information 23.1: The Förster theory of resonance energy transfer 862 Discussion questions 863 Exercises 863 Problems 864
CONTENTS xxix 24 Molecular reaction dynamics 869 25.12 Working galvanic cells Impact on technology:Fuel cell Reactive 贴雞 n theory chnology:Protecting materials 9 24.3 The material balance quation Checklist of key ideas Transition state theory 880 Further reading 951 24.4 The Eyring equation 880 on between electrode 24.5 Thermodynamic aspects 883 dynamics of molecular collisions 85 Exercises 953 24.6 Problems 955 2A月 results y su 88 Appendix 1 Quantities.units.and notational ultrafast laser techniques 892 conventions 959 Electron transfer in homogeneous systems 894 Names of quantities 4.10 The rates 959 Units 960 Notational conventions 2A12F 961 ental results 124.1 Impact on biochemistry:Electron transfer in and Further reading 962 between proteins 900 Appendix 2 Mathematical techniques 963 Further infomation 24.1:The Gibbs ene Basic procedures 963 g03 A2.1 Logarithms and exponentials Discussion questions 904 A2.2 Complex numbers and complex functions A2.3 Vectors 2 Different gration 9e5 25 Processes at solid surfaces o A2.5 Po and Taylo or expansion 9 A2.6 Partial derivatives The growth and str cture of solid surfaces 909 A2.7 Functionals and functional derivatives 910 Undetermined multipliers Surface composition 911 Differential equations The extent of adsorption 916 Statistics and probability 25.3 Physisorptionand chemisorption 916 25.4 Adsorption isotherms 917 25.5 The rates of surface processes 125.1 Impact on biochemistry:Biosensor analysis 95 Matrix algebra g75 A2.12 Matrix addition and multiplication 926 975 25.6 Mechanisms of heter A2.13 Simultaneous equations cous catalysis 927 25.7 Catalytic activity at surfaces A2.14 Eigenvalue equations 928 977 Further reading g78 lustry 929 Processes at electrodes 932 Appendix 3 Essential concepts of physics 979 25.8 The electrode-solution interface 932 25.9 The rate of charge transfer 934 Energy 979 25.10 Voltammetry 940 A3.1 Kineticand potential energy 25.11 Electrolysis 944 A3.2 Energy units
CONTENTS xxix 24 Molecular reaction dynamics 869 Reactive encounters 869 24.1 Collision theory 870 24.2 Diffusion-controlled reactions 876 24.3 The material balance equation 879 Transition state theory 880 24.4 The Eyring equation 880 24.5 Thermodynamic aspects 883 The dynamics of molecular collisions 885 24.6 Reactive collisions 886 24.7 Potential energy surfaces 887 24.8 Some results from experiments and calculations 888 24.9 The investigation of reaction dynamics with ultrafast laser techniques 892 Electron transfer in homogeneous systems 894 24.10 The rates of electron transfer processes 894 24.11 Theory of electron transfer processes 896 24.12 Experimental results 898 I24.1 Impact on biochemistry: Electron transfer in and between proteins 900 Checklist of key ideas 902 Further reading 903 Further information 24.1: The Gibbs energy of activation of electron transfer and the Marcus cross-relation 903 Discussion questions 904 Exercises 904 Problems 905 25 Processes at solid surfaces 909 The growth and structure of solid surfaces 909 25.1 Surface growth 910 25.2 Surface composition 911 The extent of adsorption 916 25.3 Physisorption and chemisorption 916 25.4 Adsorption isotherms 917 25.5 The rates of surface processes 922 I25.1 Impact on biochemistry: Biosensor analysis 925 Heterogeneous catalysis 926 25.6 Mechanisms of heterogeneous catalysis 927 25.7 Catalytic activity at surfaces 928 I25.2 Impact on technology: Catalysis in the chemical industry 929 Processes at electrodes 932 25.8 The electrode–solution interface 932 25.9 The rate of charge transfer 934 25.10 Voltammetry 940 25.11 Electrolysis 944 25.12 Working galvanic cells 945 I25.3 Impact on technology: Fuel cells 947 25.13 Corrosion 948 I25.4 Impact on technology: Protecting materials against corrosion 949 Checklist of key ideas 951 Further reading 951 Further information 25.1: The relation between electrode potential and the Galvani potential 952 Discussion questions 952 Exercises 953 Problems 955 Appendix 1 Quantities, units, and notational conventions 959 Names of quantities 959 Units 960 Notational conventions 961 Further reading 962 Appendix 2 Mathematical techniques 963 Basic procedures 963 A2.1 Logarithms and exponentials 963 A2.2 Complex numbers and complex functions 963 A2.3 Vectors 964 Calculus 965 A2.4 Differentiation and integration 965 A2.5 Power series and Taylor expansions 967 A2.6 Partial derivatives 968 A2.7 Functionals and functional derivatives 969 A2.8 Undetermined multipliers 969 A2.9 Differential equations 971 Statistics and probability 973 A2.10 Random selections 973 A2.11 Some results of probability theory 974 Matrix algebra 975 A2.12 Matrix addition and multiplication 975 A2.13 Simultaneous equations 976 A2.14 Eigenvalue equations 977 Further reading 978 Appendix 3 Essential concepts of physics 979 Energy 979 A3.1 Kinetic and potential energy 979 A3.2 Energy units 979
CONTENTS Classical mechanics 980 Electrostatics The trajectory in terms of the A3.11 The Coulomb interaction energy 980 A3.12 The Coulomb ential Newton's second law A3.13 The strength of the electric field A3.14 Electric current and power Further reading 987 The electr nagnetic field 8 A3.Refraction 984 Ans 1034 A3.10Optical activity 985 Index 1040
xxx CONTENTS Electrostatics 985 A3.11 The Coulomb interaction 986 A3.12 The Coulomb potential 986 A3.13 The strength of the electric field 986 A3.14 Electric current and power 987 Further reading 987 Data section 988 Answers to ‘b’ exercises 1028 Answers to selected problems 1034 Index 1040 Classical mechanics 980 A3.3 The trajectory in terms of the energy 980 A3.4 Newton’s second law 980 A3.5 Rotational motion 981 A3.6 The harmonic oscillator 982 Waves 983 A3.7 The electromagnetic field 983 A3.8 Features of electromagnetic radiation 983 A3.9 Refraction 984 A3.10 Optical activity 985