Quantum theory: introduction and principles ‘This chapter introduces some ofthe basic principles of quantum mecherics. First, itreviews the experimental results that overthrew the concepts of classical physics. These experi- ‘ments led to the conclusion thet particles may rot heve an arbtrary energy and that the classical concepts ct ‘partide’ and ‘wave’ blend together. The overthrow of classical ‘mechanics inspired the torruation of @ new set of conoapts and led tothe formulation of ‘quantum mocterics. In quertum mecharics, al the properties ofa eystern are expressed In ters ofa wavelunction that is obtained by sohing the Sctrcinger equation. We soo how to interpret wavefunctions. Fray, we iniroduce sore of the techriques of quantum ‘mechanics in torms of operaters, and see that they lead to the uncertainty princpo, one of the most profound deperturesfrem classical mechanics. It was once thought that the motion of atoms and subatomic particles could be expressed using classical mechanics, the laws of motion introduced in the seven teenth century by Isaac Newton, for these laws were very successful at explaining the ‘motion of everyday objects and planets. However, towards the end of the nineteenth century, experimental evidence accumulated showing that classical mechanics failed ‘when it was applied to particles as smal as electrons, and it tock until the 1920s to discover the appropriate concepts and equations for describing them. We describe the concepts ofthis new mechanics, which is called quantum mechanics, inthis chapter, and apply them throughout the remainder ofthe text. The origins of quantum mechanics ‘The basic principles of classical mechanics are reviewed in Appendix 2. In brief they show that classical physics (1) predicts a precise trajectory for particles, with precisely specified locations and momenta at each instant, and (2) allows the translational, rotational, and vibrational modes of motion to be excited to any energy simply by contolling the forces that are applied. These conclusions agree with everyday experi- ence. Everyday experience, however, does not extend to individual atoms, and careful experiments of the type described below have shown that classical mechanics fails ‘when applied to the transfers of very small energies and to objects of very stall mass, ‘We shall also investigate the poperies flight. n classical physics, lights described 4s electromagnetic radiation, which is understood in terms of the electromagnetic field, an oscillating electric and magnetic disturbance that spreads as aharmonic wave through empty space, the vacuum. Such waves are generated by the acceleration ‘of electric charge, asin the oscillating motion of electrons inthe antenna of a radio ‘transmitter. The wave travels at a constant speed called the speed of light, c, which ‘The origins of quantum mechanics 181 The failures of classical physics 182 Wave- particle duality 18.1 Impact on biology: Electron microscopy ‘The dynamics of microscopic systems £83 The Schrodinger equation {84 The Born interpretation ofthe wavefunction ‘Quantum mechanical principles {85 Theinformationina wavefunction ‘86 The uncertainty principle 18.7 The postulates of quantum smechanies (Checklist of key dees Further reocing Discussion questions Breciees robles244 8 QUANTUM THEORY: INTRODUCTION AND PRINCIPLES Wavelength, 2 a 2 / } Fa.81 ‘The wavelength, 2 ofa wave isthe peak-to-peak distance (b) The waveis shown travelling tothe right at a speed ‘Atagiven location, the instantaneous ‘amplitude ofthe wave changes through a ‘complete cyee (the four dots show hala «yee. The frequency, vis the number of cycles per second that occur at given point. Comment 8.1 Harmonic waves are waves with isplacements that can be expressed as sine or cosine functions. The physics of ‘waves is reviewed in Appendix 3. is about 3 x 10" ms. As its name suggests, an electromagnetic field has two com ponents, an electric field that acts on charged particles (whether stationary or ‘moving) and a magnetic field that acts only on moving charged particles. The elec- ‘tromagnetic field is characterized by a wavelength, 2 (lambda), the distance between the neighbouring peaks of the wave, and its frequency, v (nu), the number of times pper second at which its displacement at a fixed point returns to its original value (Fig. 8.1). The frequency is measured in hertz, where 1 Hz= 1 5". The wavelength and frequency of an electromagnetic wave are related by =e a) ‘Therefore, the shorter the wavelength, the higher the frequency. The characteristics of the wave are also reported by giving the wavenumber, (nu tilde), of the radiation, where ? : 8.2 7 82) ‘Wavenumbers are normally reported in reciprocal centimetres (em). Figure 8.2 summarizes the electromagnetic spectrum, the description and classi- fication ofthe electromagnetic field aecording to its frequency and wavelength. White light is a mixture of electromagnetic radiation with wavelengths ranging from about 380 nm to about 700 nm (1 nm = 10°? m). Our eyes perceive different wavelengths (of radiation in this range as different colours, soit can be said that white light is a ‘mixture of ight ofall different colours. ‘The wave model falls short of describing all the properties of radiation. So, just as cour view of particles (and in particular small particles) needs to be adjusted, a new view of light also has to be developed 81 The failures of classical physics In this section we review some of the experimental evidence that showed that several concepts of classical mechanics are untenable. In particular, we shall see that observa~ tions of the radiation emitted by hot bodies, heat capacities, and the spectra of atoms and molecules indicate that systems can take up energy only in discrete amounts. {@) Black-body radiation A hot object emits electromagnetic radiation. At high temperatures, an appreciable proportion of the radiation is in the visible region of the spectrum, and a higher ‘Wavelengthim 1 10° 10" 107 10* 10° 10 10° 10% 10° 10" 10° 10” 10° 10% gi AGE 5 g € 4 g & ge 5 SECSIeSInE Ss Ea ESE | Mi Fer side ce fio | Micro- r, | BE Vacuum ae sosmic Resto | Move | interes | SE | Mig|uteaic| XY fer ye Molecular Molecular Eleetronie Core-electron Nuclear rotation Vibration excitation excitation excitation "9.82 The dectromagneticspectrum and the classification ofthe spectral regions.8.1 THE FAILURES OF CLASSICAL PHYSICS 245, proportion of short wavelength blue light is generated asthe emperture i used This behicur iste when heared ion br lowing re bot besores white hat ‘when heated further. The dependence is illustrated in Fig. 83, which shows how the {nergy output varie with wavelength at several temperatures. Te curves ae thore of an ideal emitter called a black body, which is an object capable of emitting and absorbing all frequencies of radiation uniformly. A good approximation to a black Tal plea cpt ontaernaiaie ote fcote|temmetne, because any radiation leaking out of tbe hol as ben abyorbed and e-emited inside so many nes that thas come to thermal equilibrium with he wal (Fig 84), Tit cepaaiton fa bey set a afoc cabenge areaceeat ery area a ere ed beret ce ea ‘asia physi. The physicist Lord Rayeigh studied i theorctially for a claical viewpoiat and thought ofthe dectromagnetc fed a a collection of oxclators of A pouuble Hequences He regarded the prescoce of radiation of fiequeney (end therefore of wavelength A = civ) as signifying that the electromagnetic oscillator of that frequency had been excited (Fig. 8.5). Rayleigh used the equipartition principle (ection 2.2) to calculate the average energy ofeach oscillatoraskT.'Then, with minor hhelp from James Jeans, he arrived at the Rayleigh-Jeans law (see Further reading for its justification): a pe (3) pik pas where p (tho), the density of states, is the proportionality constant between 2. and the energy density, d, in the range of wavelengths between A and 2+ d, kis Boltzmann's constant (k= 1.381 x 10 ] K~!). The units of p are typically joules per metre (m+), to give an energy density din joules per cubic metre (J n>) when ‘amliplicd by a wavelongals rats et enctres A Sag lenailyof seated af I wa Teng A cinly means cha er la ot of encry ociatd with wevlengta yng, between Zand A-+d2. The total energy density (in joules per cubic metre) ina region if by incgreing 89 ver el Waele betwee sea aay ed the total energy (in joules) within the region is obtained by multiplying that total energy denatyby the volume ofthe elon. ct ieee Detected rdiation Pinhole af Container at 2 ‘temperature T an be F.84 An experimental representation ofa regarded as abe to suppert oscillations black-bod isa pinhole inan otherwise ‘of the electromagnetic eld, Wher high ‘losed container. Theradiation iseflected frequency, short wavelength oscillator ‘any times within the container and (a) isexcited, that frequency of a comesto thermal equilibrium withthe is present. The presence oflow frequency, walls ata temperature T: Radiation leaking long wavelength radiation (b) signifies ‘out through the pinholes characteristic that an oscillator ofthe corresponding, ‘of the radiation inthe container. frequency has been excited Veuve Energy distribution, Wavelength, 2 1g.03 The energy distribution ina black body cavity at several temperatures. Note how the energy density increases in the tegion of shorter wavelengths asthe temperature istaised, and how the peak shifts to shorter wavelengths, The total cenengy density (the area under the curve) Increases asthe temperature is increased (sT9.