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量子力學發展史 近代科學發展之三 物理模型 粒子模型 • Allowed us to ignore unnecessary details of an object when studying its behavior 系統與剛體 • Extension of particle model 波動模型 兩種新模型 • • 量子粒子 邊界條件下的量子粒子 黑體幅射 物體在任何溫度下皆會發出熱幅射(電磁 幅射) 電磁幅射波長會隨物體表面溫度的變化 而改變 黑體為一理想系統會吸收所有射入的幅射 由黑體發射出的電磁幅射稱為幅射 黑體近似 黑體模型可近似為開 了一小孔洞的金屬空 腔 離開空腔的電磁幅射 其性質將只與空腔的 表面溫度有關 黑體實驗結論 幅射的總功率與溫度的關係滿足Stefan定律 • Stefan’s Law • P = s A e T4 • For a blackbody, e = 1 s is the Stefan-Boltzmann constant s = 5.670 x 10-8 W / m2 . K4 波長分佈曲線的峰值位置隨溫度升高兒而往短 波長方向偏移,Wien位移定律 • Wien’s displacement law lmax T = 2.898 x 10-3 m.K 黑體幅射強度隨波長的分佈 l l 幅射強度隨溫度升高 而增強 總幅射量隨溫度升高 而變大 • The area under the curve 峰值對應的波長隨 溫度升高而變短 紫外危機 古典物理的預測與實驗 在短波處的結果發生極 大的差異 此現象稱為紫外危機, 尤其古典物理預測當幅 射波的波長趨近於零時 更會得到無限大的能量, 此與實驗觀察完全相反 Max Planck(拯救紫外危機的英雄) 1858 – 1947 He introduced the concept of “quantum of action” In 1918 he was awarded the Nobel Prize for the discovery of the quantized nature of energy Planck’s Theory of Blackbody Radiation In 1900, Planck developed a structural model for blackbody radiation that leads to an equation in agreement with the experimental results He assumed the cavity radiation came from atomic oscillations in the cavity walls Planck made two assumptions about the nature of the oscillators in the cavity walls Planck’s Theory of Blackbody Radiation In 1900, Planck developed a structural model for blackbody radiation that leads to an equation in agreement with the experimental results He assumed the cavity radiation came from atomic oscillations in the cavity walls Planck made two assumptions about the nature of the oscillators in the cavity walls Planck’s Assumption, 1 The energy of an oscillator can have only certain discrete values En • • • En = n h ƒ • n is a positive integer called the quantum number • h is Planck’s constant • ƒ is the frequency of oscillation This says the energy is quantized Each discrete energy value corresponds to a different quantum state Planck’s Assumption, 2 The oscillators emit or absorb energy only in discrete units They do this when making a transition from one quantum state to another • • The entire energy difference between the initial and final states in the transition is emitted or absorbed as a single quantum of radiation An oscillator emits or absorbs energy only when it changes quantum states Energy-Level Diagram An energy-level diagram shows the quantized energy levels and allowed transitions Energy is on the vertical axis Horizontal lines represent the allowed energy levels The double-headed arrows indicate allowed transitions Correspondence Principle (對應原理) 當量子系統的量子態總數變大時,量子現象應 當會連續地轉變成古典現象 • • Quantum effects are not seen on an everyday basis since the energy change is too small a fraction of the total energy Quantum effects are important and become measurable only on the submicroscopic level of atoms and molecules Photoelectric Effect The photoelectric effect occurs when light incident on certain metallic surfaces causes electrons to be emitted from those surfaces • The emitted electrons are called photoelectrons The effect was first discovered by Hertz Photoelectric Effect Apparatus When the tube is kept in the dark, the ammeter reads zero When plate E is illuminated by light having an appropriate wavelength, a current is detected by the ammeter The current arises from photoelectrons emitted from the negative plate (E) and collected at the positive plate (C) Photoelectric Effect, Results At large values of DV, the current reaches a maximum value • All the electrons emitted at E are collected at C The maximum current increases as the intensity of the incident light increases When DV is negative, the current drops When DV is equal to or more negative than DVs, the current is zero Photoelectric Effect Feature 1 Dependence of photoelectron kinetic energy on light intensity • Classical Prediction • Electrons should absorb energy continually from the • • electromagnetic waves As the light intensity incident on the metal is increased, the electrons should be ejected with more kinetic energy Experimental Result • The maximum kinetic energy is independent of light • intensity The current goes to zero at the same negative voltage for all intensity curves Photoelectric Effect Feature 2 Time interval between incidence of light and ejection of photoelectrons • Classical Prediction • For very weak light, a measurable time interval should • • pass between the instant the light is turned on and the time an electron is ejected from the metal This time interval is required for the electron to absorb the incident radiation before it acquires enough energy to escape from the metal Experimental Result • Electrons are emitted almost instantaneously, even at • very low light intensities Less than 10-9 s Photoelectric Effect Feature 3 Dependence of ejection of electrons on light frequency • • Classical Prediction • Electrons should be ejected at any frequency as long as the light intensity is high enough Experimental Result • No electrons are emitted if the incident light falls below • • some cutoff frequency, ƒc The cutoff frequency is characteristic of the material being illuminated No electrons are ejected below the cutoff frequency regardless of intensity Photoelectric Effect Feature 4 Dependence of photoelectron kinetic energy on light frequency • Classical Prediction • There should be no relationship between the frequency • • of the light and the electric kinetic energy The kinetic energy should be related to the intensity of the light Experimental Result • The maximum kinetic energy of the photoelectrons increases with increasing light frequency Photoelectric Effect Features, Summary The experimental results contradict all four classical predictions Einstein extended Planck’s concept of quantization to electromagnetic waves All electromagnetic radiation can be considered a stream of quanta, now called photons A photon of incident light gives all its energy hƒ to a single electron in the metal Photoelectric Effect, Work Function Electrons ejected from the surface of the metal and not making collisions with other metal atoms before escaping possess the maximum kinetic energy Kmax Kmax = hƒ – f f is called the work function • The work function represents the minimum energy with which an electron is bound in the metal Some Work Function Values Photon Model Explanation of the Photoelectric Effect Dependence of photoelectron kinetic energy on light intensity • • • Kmax is independent of light intensity K depends on the light frequency and the work function The intensity will change the number of photoelectrons being emitted, but not the energy of an individual electron Time interval between incidence of light and ejection of the photoelectron • Each photon can have enough energy to eject an electron immediately Photon Model Explanation of the Photoelectric Effect, cont Dependence of ejection of electrons on light frequency • There is a failure to observe photoelectric • effect below a certain cutoff frequency, which indicates the photon must have more energy than the work function in order to eject an electron Without enough energy, an electron cannot be ejected, regardless of the light intensity Photon Model Explanation of the Photoelectric Effect, final Dependence of photoelectron kinetic energy on light frequency • Since Kmax = hƒ – f • As the frequency increases, the kinetic energy will increase • Once the energy of the work function is exceeded • There is a linear relationship between the kinetic energy and the frequency Cutoff Frequency The lines show the linear relationship between K and ƒ The slope of each line is h The absolute value of the yintercept is the work function The x-intercept is the cutoff frequency • This is the frequency below which no photoelectrons are emitted Cutoff Frequency and Wavelength The cutoff frequency is related to the work function through ƒc = f / h The cutoff frequency corresponds to a cutoff wavelength c hc lc ƒc f Wavelengths greater than lc incident on a material having a work function f do not result in the emission of photoelectrons Applications of the Photoelectric Effect Detector in the light meter of a camera Phototube • Used in burglar alarms and soundtrack of • motion picture films Largely replaced by semiconductor devices Photomultiplier tubes • Used in nuclear detectors and astronomy Arthur Holly Compton 1892 - 1962 Director at the lab of the University of Chicago Discovered the Compton Effect Shared the Nobel Prize in 1927 The Compton Effect, Introduction Compton and coworkers dealt with Einstein’s idea of photon momentum • Einstein proposed a photon with energy E carries a momentum of E/c = hƒ / c Compton and others accumulated evidence of the inadequacy of the classical wave theory The classical wave theory of light failed to explain the scattering of x-rays from electrons Compton Effect, Classical Predictions According to the classical theory, electromagnetic waves of frequency ƒo incident on electrons should • • Accelerate in the direction of propagation of the x-rays by radiation pressure Oscillate at the apparent frequency of the radiation since the oscillating electric field should set the electrons in motion Overall, the scattered wave frequency at a given angle should be a distribution of Dopplershifted values Compton Effect, Observations Compton’s experiments showed that, at any given angle, only one frequency of radiation is observed Compton Effect, Explanation The results could be explained by treating the photons as point-like particles having energy hƒ and momentum hƒ / c Assume the energy and momentum of the isolated system of the colliding photon-electron are conserved • Adopted a particle model for a well-known wave This scattering phenomena is known as the Compton Effect Compton Shift Equation The graphs show the scattered x-ray for various angles The shifted peak, l', is caused by the scattering of free electrons • h l 'islcalled cos shift 1Compton o This the me c equation Compton Wavelength The unshifted wavelength, lo, is caused by x-rays scattered from the electrons that are tightly bound to the target atoms The shifted peak, l', is caused by x-rays scattered from free electrons in the target The Compton wavelength is h 0.00243 nm me c Photons and Waves Revisited Some experiments are best explained by the photon model Some are best explained by the wave model We must accept both models and admit that the true nature of light is not describable in terms of any single classical model Light has a dual nature in that it exhibits both wave and particle characteristics The particle model and the wave model of light complement each other Louis de Broglie 1892 – 1987 Originally studied history Was awarded the Nobel Prize in 1929 for his prediction of the wave nature of electrons Wave Properties of Particles Louis de Broglie postulated that because photons have both wave and particle characteristics, perhaps all forms of matter have both properties The de Broglie wavelength of a particle is h h l p mv Frequency of a Particle In an analogy with photons, de Broglie postulated that particles would also have a frequency associated with them E ƒ h These equations present the dual nature of matter • • particle nature, m and v wave nature, l and ƒ Davisson-Germer Experiment If particles have a wave nature, then under the correct conditions, they should exhibit diffraction effects Davission and Germer measured the wavelength of electrons This provided experimental confirmation of the matter waves proposed by de Broglie Electron Microscope The electron microscope depends on the wave characteristics of electrons The electron microscope has a high resolving power because it has a very short wavelength Typically, the wavelengths of the electrons are about 100 times shorter than that of visible light Quantum Particle The quantum particle is a new simplification model that is a result of the recognition of the dual nature of light and of material particles In this model, entities have both particle and wave characteristics We much choose one appropriate behavior in order to understand a particular phenomenon Ideal Particle vs. Ideal Wave An ideal particle has zero size An ideal wave has a single frequency and is infinitely long • Therefore, it is localized in space • Therefore, it is unlocalized in space A localized entity can be built from infinitely long waves Particle as a Wave Packet Multiple waves are superimposed so that one of its crests is at x = 0 The result is that all the waves add constructively at x = 0 There is destructive interference at every point except x = 0 The small region of constructive interference is called a wave packet • The wave packet can be identified as a particle Wave Envelope The blue line represents the envelope function This envelope can travel through space with a different speed than the individual waves Speeds Associated with Wave Packet The phase speed of a wave in a wave packet is given by v phase • This is the rate of advance of a crest on a k single wave The group speed is given by v g d dk of the wave packet itself • This is the speed Speeds, cont The group speed can also be expressed in terms of energy and momentum dE d p2 1 vg 2p u dp dp 2m 2m This indicates that the group speed of the wave packet is identical to the speed of the particle that it is modeled to represent Electron Diffraction, Set-Up Electron Diffraction, Experiment Parallel beams of mono-energetic electrons are incident on a double slit The slit widths are small compared to the electron wavelength An electron detector is positioned far from the slits at a distance much greater than the slit separation Electron Diffraction, cont If the detector collects electrons for a long enough time, a typical wave interference pattern is produced This is distinct evidence that electrons are interfering, a wave-like behavior The interference pattern becomes clearer as the number of electrons reaching the screen increases Electron Diffraction, Equations A minimum occurs when d sin l 2 or h sin 2 px d This shows the dual nature of the electron • • The electrons are detected as particles at a localized spot at some instant of time The probability of arrival at that spot is determined by finding the intensity of two interfering waves Electron Diffraction, Closed Slits If one slit is closed, the maximum is centered around the opening Closing the other slit produces another maximum centered around that opening The total effect is the blue line It is completely different from the interference pattern (brown curve) Electron Diffraction Explained An electron interacts with both slits simultaneously If an attempt is made to determine experimentally which slit the electron goes through, the act of measuring destroys the interference pattern • It is impossible to determine which slit the electron goes through In effect, the electron goes through both slits • The wave components of the electron are present at both slits at the same time Werner Heisenberg 1901 – 1976 Developed matrix mechanics Many contributions include • • • Uncertainty Principle • Rec’d Nobel Prize in 1932 Prediction of two forms of molecular hydrogen Theoretical models of the nucleus The Uncertainty Principle, Introduction In classical mechanics, it is possible, in principle, to make measurements with arbitrarily small uncertainty Quantum theory predicts that it is fundamentally impossible to make simultaneous measurements of a particle’s position and momentum with infinite accuracy Heisenberg Uncertainty Principle, Statement The Heisenberg Uncertainty Principle states if a measurement of the position of a particle is made with uncertainty Dx and a simultaneous measurement of its x component of momentum is made with uncertainty Dp, the product of the two uncertainties can never be smaller than DxDp x 2 Heisenberg Uncertainty Principle, Explained It is physically impossible to measure simultaneously the exact position and exact momentum of a particle The inescapable uncertainties do not arise from imperfections in practical measuring instruments The uncertainties arise from the quantum structure of matter Heisenberg Uncertainty Principle, Another Form Another form of the Uncertainty Principle can be expressed in terms of energy and time DEDt 2 This suggests that energy conservation can appear to be violated by an amount DE as long as it is only for a short time interval Dt Probability – A Particle Interpretation From the particle point of view, the probability per unit volume of finding a photon in a given region of space at an instant of time is proportional to the number N of photons per unit volume at that time and to the intensity Probability N I V V Probability – A Wave Interpretation From the point of view of a wave, the intensity of electromagnetic radiation is proportional to the square of the electric field amplitude, E I E 2 Combining the points of view gives Probability E2 V Probability – Interpretation Summary For electromagnetic radiation, the probability per unit volume of finding a particle associated with this radiation is proportional to the square of the amplitude of the associated em wave • The particle is the photon The amplitude of the wave associated with the particle is called the probability amplitude or the wave function • The symbol is Y Wave Function The complete wave function Y for a system depends on the positions of all the particles in the system and on time • The function can be written as Y(r1, r2, … rj…., t) = y(rj)e-it • rj is the position of the jth particle in the system = 2 p ƒ is the angular frequency • i 1 Wave Function, con’t The wave function is often complex-valued The absolute square |y|2 = y*y is always real and positive y* is the complete conjugate of y • It is proportional to the probability per unit volume of finding a particle at a given point at some instant The wave function contains within it all the information that can be known about the particle Wave Function, General Comments, Final The probabilistic interpretation of the wave function was first suggested by Max Born Erwin Schrödinger proposed a wave equation that describes the manner in which the wave function changes in space and time • This Schrödinger Wave Equation represents a key element in quantum mechanics Wave Function of a Free Particle The wave function of a free particle moving along the x-axis can be written as y(x) = Aeikx • • k = 2 p / l is the angular wave number of the wave representing the particle A is the constant amplitude If y represents a single particle, |y|2 is the relative probability per unit volume that the particle will be found at any given point in the volume • |y|2 is called the probability density Wave Function of a Free Particle, Cont In general, the probability of finding the particle in a volume dV is |y|2 dV With one-dimensional analysis, this becomes |y|2 dx The probability of finding the particle in the arbitrary interval axb is Pab a y 2 dx b and is the area under the curve Wave Function of a Free Particle, Final Because the particle must be somewhere along the x axis, the sum of all the probabilities over all values of x must be 1 Pab y dx 1 2 • Any wave function satisfying this equation is • said to be normalized Normalization is simply a statement that the particle exists at some point in space Expectation Values y is not a measurable quantity Measurable quantities of a particle can be derived from y The average position is called the expectation value of x and is defined as x y * xydx Expectation Values, cont The expectation value of any function of x can also be found f x y * f x ydx • The expectation values are analogous to averages Particle in a Box A particle is confined to a one-dimensional region of space • The “box” is onedimensional The particle is bouncing elastically back and forth between two impenetrable walls separated by L Classically, the particle’s momentum and kinetic energy remain constant Wave Function for the Particle in a Box Since the walls are impenetrable, there is zero probability of finding the particle outside the box y(x) = 0 for x < 0 and x > L The wave function must also be 0 at the walls • The function must be continuous y(0) = 0 and y(L) = 0 Potential Energy for a Particle in a Box As long as the particle is inside the box, the potential energy does not depend on its location • We can choose this energy value to be zero The energy is infinitely large if the particle is outside the box • This ensures that the wave function is zero outside the box Wave Function of a Particle in a Box – Mathematical The wave function can be expressed as a real, sinusoidal function 2p x y ( x ) A sin l Applying the boundary conditions and using the de Broglie wavelength np x y ( x ) A sin L Graphical Representations for a Particle in a Box Wave Function of the Particle in a Box, cont Only certain wavelengths for the particle are allowed |y|2 is zero at the boundaries |y|2 is zero at other locations as well, depending on the values of n The number of zero points increases by one each time the quantum number increases by one Momentum of the Particle in a Box Remember the wavelengths are restricted to specific values Therefore, the momentum values are also restricted h nh p l 2L Energy of a Particle in a Box We chose the potential energy of the particle to be zero inside the box Therefore, the energy of the particle is just its kinetic energy h2 2 En n 2 8mL n 1, 2, 3 The energy of the particle is quantized Energy Level Diagram – Particle in a Box The lowest allowed energy corresponds to the ground state En = n2E1 are called excited states E = 0 is not an allowed state The particle can never be at rest The lowest energy the particle can have, E = 1, is called the zero-point energy Boundary Conditions Boundary conditions are applied to determine the allowed states of the system In the model of a particle under boundary conditions, an interaction of a particle with its environment represents one or more boundary conditions and, if the interaction restricts the particle to a finite region of space, results in quantization of the energy of the system In general, boundary conditions are related to the coordinates describing the problem Erwin Schrödinger 1887 – 1961 Best known as one of the creators of quantum mechanics His approach was shown to be equivalent to Heisenberg’s Also worked with • • • statistical mechanics color vision general relativity Schrödinger Equation The Schrödinger equation as it applies to a particle of mass m confined to moving along the x axis and interacting with its environment through a potential energy function U(x) is h2 d 2y Uy Ey 2 2m dx This is called the time-independent Schrödinger equation Schrödinger Equation, cont Both for a free particle and a particle in a box, the first term in the Schrödinger equation reduces to the kinetic energy of the particle multiplied by the wave function Solutions to the Schrödinger equation in different regions must join smoothly at the boundaries Schrödinger Equation, final y(x) must be continuous y(x) must approach zero as x approaches ± • This is needed so that y(x) obeys the normalization condition dy / dx must also be continuous for finite values of the potential energy Solutions of the Schrödinger Equation Solutions of the Schrödinger equation may be very difficult The Schrödinger equation has been extremely successful in explaining the behavior of atomic and nuclear systems • Classical physics failed to explain this behavior When quantum mechanics is applied to macroscopic objects, the results agree with classical physics Potential Wells A potential well is a graphical representation of energy The well is the upward-facing region of the curve in a potential energy diagram The particle in a box is sometimes said to be in a square well • Due to the shape of the potential energy diagram Schrödinger Equation Applied to a Particle in a Box In the region 0 < x < L, where U = 0, the Schrödinger equation can be expressed in the form d 2y 2mE 2 y k y 2 2 dx The most general solution to the equation is y(x) = A sin kx + B cos kx • A and B are constants determined by the boundary and normalization conditions Schrödinger Equation Applied to a Particle in a Box, cont. Solving for the allowed energies gives h2 2 En n 2 8mL The allowed wave functions are given by • • 2 np x np x y ( x ) A sin sin L L L The second expression is the normalized wave function These match the original results for the particle in a box Application – Nanotechnology Nanotechnology refers to the design and application of devices having dimensions ranging from 1 to 100 nm Nanotechnology uses the idea of trapping particles in potential wells One area of nanotechnology of interest to researchers is the quantum dot • • A quantum dot is a small region that is grown in a silicon crystal that acts as a potential well Storage of binary information using quantum dots is being researched Quantum Corral Corrals and other structures are used to confine surface electron waves This corral is a ring of 48 iron atoms on a copper surface The ring has a diameter of 143 nm Tunneling The potential energy has a constant value U in the region of width L and zero in all other regions This a called a square barrier U is the called the barrier height Tunneling, cont Classically, the particle is reflected by the barrier • Regions II and III would be forbidden According to quantum mechanics, all regions are accessible to the particle • • The probability of the particle being in a classically forbidden region is low, but not zero According to the Uncertainty Principle, the particle can be inside the barrier as long as the time interval is short and consistent with the Principle Tunneling, final The curve in the diagram represents a full solution to the Schrödinger equation Movement of the particle to the far side of the barrier is called tunneling or barrier penetration The probability of tunneling can be described with a transmission coefficient, T, and a reflection coefficient, R Tunneling Coefficients The transmission coefficient represents the probability that the particle penetrates to the other side of the barrier The reflection coefficient represents the probability that the particle is reflected by the barrier T+R=1 • • The particle must be either transmitted or reflected T e-2CL and can be non zero Tunneling is observed and provides evidence of the principles of quantum mechanics Applications of Tunneling Alpha decay • In order for the alpha particle to escape from the nucleus, it must penetrate a barrier whose energy is several times greater than the energy of the nucleus-alpha particle system Nuclear fusion • Protons can tunnel through the barrier caused by their mutual electrostatic repulsion More Applications of Tunneling – Scanning Tunneling Microscope An electrically conducting probe with a very sharp edge is brought near the surface to be studied The empty space between the tip and the surface represents the “barrier” The tip and the surface are two walls of the “potential well” The vertical motion of the probe follows the contour of the specimen’s surface and therefore an image of the surface is obtained Cosmic Temperature In the 1940’s, a structural model of the universe was developed which predicted the existence of thermal radiation from the Big Bang • The radiation would now have a wavelength • distribution consistent with a black body The temperature would be a few kelvins Cosmic Temperature, cont In 1965 two workers at Bell Labs found a consistent “noise” in the radiation they were measuring • They were detecting the background radiation • • from the Big Bang It was detected by their system regardless of direction It was consistent with a back body at about 3 K Cosmic Temperature, Final Measurements at many wavelengths were needed The brown curve is the theoretical curve The blue dots represent measurements from COBE and Bell Labs