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Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Chapter 7 Quantum Theory and Atomic Structure 7-1 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Quantum Theory and Atomic Structure 7.1 The Nature of Light 7.2 Atomic Spectra 7.3 The Wave-Particle Duality of Matter and Energy 7.4 The Quantum-Mechanical Model of the Atom 7-2 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. The Wave Nature of Light Figure 7.1 Frequency and Wavelength c=ln 7-3 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.2 7-4 Amplitude (intensity) of a wave. Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.3 7-5 Regions of the electromagnetic spectrum. Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Sample Problem 7.1 PROBLEM: PLAN: Interconverting Wavelength and Frequency Use c = ln wavelength in units given o 1 A = 10-10 m 1 cm = 10-2 m 1 nm = 10-9 m wavelength in m n = c/l frequency (s-1 or Hz) 7-6 o A dental hygienist uses x-rays (l= 1.00A) to take a series of dental radiographs while the patient listens to a radio station (l = 325 cm) and looks out the window at the blue sky (l= 473 nm). What is the frequency (in s-1) of the electromagnetic radiation from each source? (Assume that the radiation travels at the speed of light, 3.00x108 m/s.) SOLUTION: o -10 -10 1.00A 10 o m = 1.00x10 m 1A 3x108 m/s = 3x1018 s-1 n= 1.00x10-10 m -2 325 cm 10 m = 325x10-2 m 1 cm 3x108 m/s n= = 9.23x107 s-1 325x10-2 m 10-9 m 473nm = 473x10-9 m 1 nm 3x108 m/s = 6.34x1014 s-1 n= 473x10-9 m Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.4 Different behaviors of waves and particles. 7-7 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. The diffraction pattern caused by light passing through two adjacent slits. Figure 7.5 7-8 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.6 Demonstration of the photoelectric effect. 7-9 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Sample Problem 7.2 Calculating the Energy of Radiation from Its Wavelength PROBLEM: A cook uses a microwave oven to heat a meal. The wavelength of the radiation is 1.20cm. What is the energy of one photon of this microwave radiation? PLAN: After converting cm to m, we can use the energy equation, E = hn combined with n = c/l to find the energy. SOLUTION: E= E = hc/l 6.626X10-34J*s x 3x108m/s 1.20cm 10-2m cm 7-10 = 1.66x10-23J Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.7 The line spectra of several elements. 7-11 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Rydberg equation 1 l = R 1 n12 1 n22 R is the Rydberg constant = 1.096776x107 m-1 Figure 7.8 Three series of spectral lines of atomic hydrogen. for the visible series, n1 = 2 and n2 = 3, 4, 5, ... 7-12 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.9 Quantum staircase. 7-13 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.10 The Bohr explanation of the three series of spectral lines. 7-14 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.13 Wave motion in restricted systems. 7-15 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. l = h /mu Table 7.1 The de Broglie Wavelengths of Several Objects Substance Speed (m/s) l (m) slow electron 9x10-28 fast electron 9x10-28 5.9x106 1x10-10 alpha particle 6.6x10-24 1.5x107 7x10-15 one-gram mass 1.0 0.01 7x10-29 baseball 142 25.0 2x10-34 6.0x1027 3.0x104 4x10-63 Earth 7-16 Mass (g) 1.0 7x10-4 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Sample Problem 7.3 Calculating the de Broglie Wavelength of an Electron PROBLEM: Find the deBroglie wavelength of an electron with a speed of 1.00x106m/s (electron mass = 9.11x10-31kg; h = 6.626x10-34 kg*m2/s). PLAN: Knowing the mass and the speed of the electron allows to use the equation l = h/mu to find the wavelength. SOLUTION: l= 6.626x10-34kg*m2/s 9.11x10-31kg x 1.00x106m/s 7-17 = 7.27x10-10m Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.14 Comparing the diffraction patterns of x-rays and electrons. x-ray diffraction of aluminum foil 7-18 electron diffraction of aluminum foil Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.15 CLASSICAL THEORY Matter particulate, massive Energy continuous, wavelike Summary of the major observations and theories leading from classical theory to quantum theory. Since matter is discontinuous and particulate perhaps energy is discontinuous and particulate. Observation blackbody radiation 7-19 Theory Planck: photoelectric effect Energy is quantized; only certain values allowed Einstein: Light has particulate behavior (photons) atomic line spectra Bohr: Energy of atoms is quantized; photon emitted when electron changes orbit. Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.15 continued Since energy is wavelike perhaps matter is wavelike Observation Davisson/Germer: electron diffraction by metal crystal Theory deBroglie: All matter travels in waves; energy of atom is quantized due to wave motion of electrons Since matter has mass perhaps energy has mass Observation Compton: photon wavelength increases (momentum decreases) after colliding with electron Theory Einstein/deBroglie: Mass and energy are equivalent; particles have wavelength and photons have momentum. QUANTUM THEORY Energy same as Matter particulate, massive, wavelike 7-20 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. The Heisenberg Uncertainty Principle Dx * mDu ≥ 7-21 h 4p Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. The Schrödinger Equation HY = EY wave function d2Y dx2 + d2Y dy2 mass of electron + d2Y dz2 how y changes in space 7-22 potential energy at x,y,z 8p2mQ + (E-V(x,y,z)Y(x,y,z) = 0 2 h total quantized energy of the atomic system Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.16 Electron probability in the ground-state H atom. 7-23 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Quantum Numbers and Atomic Orbitals An atomic orbital is specified by three quantum numbers. n the principal quantum number - a positive integer l the angular momentum quantum number - an integer from 0 to n-1 ml the magnetic moment quantum number - an integer from -l to +l 7-24 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Table 7.2 The Hierarchy of Quantum Numbers for Atomic Orbitals Name, Symbol (Property) Allowed Values Quantum Numbers Principal, n Positive integer (size, energy) (1, 2, 3, ...) 1 Angular momentum, l 0 to n-1 (shape) 0 0 0 0 Magnetic, ml -l,…,0,…,+l (orientation) 2 3 1 0 2 0 -1 0 +1 -1 0 +1 -2 7-25 1 -1 0 +1 +2 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Sample Problem 7.4 Determining Quantum Numbers for an Energy Level PROBLEM: What values of the angular momentum (l) and magnetic (ml) quantum numbers are allowed for a principal quantum number (n) of 3? How many orbitals are allowed for n = 3? PLAN: Follow the rules for allowable quantum numbers found in the text. l values can be integers from 0 to n-1; ml can be integers from -l through 0 to + l. SOLUTION: For n = 3, l = 0, 1, 2 For l = 0 ml = 0 For l = 1 ml = -1, 0, or +1 For l = 2 ml = -2, -1, 0, +1, or +2 There are 9 ml values and therefore 9 orbitals with n = 3. 7-26 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Sample Problem 7.5 Determining Sublevel Names and Orbital Quantum Numbers PROBLEM: Give the name, magnetic quantum numbers, and number of orbitals for each sublevel with the following quantum numbers: (a) n = 3, l = 2 (b) n = 2, l = 0 (c) n = 5, l = 1 (d) n = 4, l = 3 PLAN: Combine the n value and l designation to name the sublevel. Knowing l, we can find ml and the number of orbitals. SOLUTION: n l (a) 3 2 3d -2, -1, 0, 1, 2 5 (b) 2 0 2s 0 1 (c) 5 1 5p -1, 0, 1 3 (d) 4 3 4f -3, -2, -1, 0, 1, 2, 3 7 7-27 sublevel name possible ml values # of orbitals Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.18 7-28 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.19 7-29 The 2p orbitals. Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.20 7-30 The 3d orbitals. Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.20 continued 7-31 Copyright ©The McGraw-Hill Companies, Inc. Permission required for reproduction or display. Figure 7.21 7-32 One of the seven possible 4f orbitals.