4/5/2010. Covalent Bonding: Orbitals. Figure 14.25: The combination of hydrogen 1s atomic orbitals to form MOs - = 0
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1 Figure 13.1: (a) The interaction of two hydrogen atoms (b) Energy profile as a function of the distance between the nuclei of the hydrogen atoms. Covalent Bonding: Orbitals b Copyright Houghton Mifflin Company. All rights reserved. 14a 2 Figure 13.1: (a) The interaction of two hydrogen atoms (b) Energy profile as a function of the distance between the nuclei of the hydrogen atoms. Figure 14.25: The combination of hydrogen 1s atomic orbitals to form MOs Copyright Houghton Mifflin Company. All rights reserved. 14a 3 Copyright Houghton Mifflin Company. All rights reserved. 14a 4 - (- sign flips phase of the sound wave function) - = Copyright Houghton Mifflin Company. All rights reserved. 14a 5 Auto mufflers use destructive interference of sound waves to reduce engine noises. Copyright Houghton Mifflin Company. All rights reserved. 14a 6 1
2 Bose is $200. Want to do it yourself? See Web site. Copyright Houghton Mifflin Company. All rights reserved. 14a 7 Copyright Houghton Mifflin Company. All rights reserved. 14a 8 An analogy between light waves and atomic wave functions. Figure 14.26: (a) The MO energy-level diagram for the H2 molecule (b) The shapes of the Mos are obtained by squaring the wave functions for MO1 and MO2. NOTE: +/- signs show PHASES of waves, NOT CHARGES! Amplitudes of wave functions added Amplitudes of wave functions subtracted. Copyright Houghton Mifflin Company. All rights reserved. 14a 11 Copyright Houghton Mifflin Company. All rights reserved. 14a 12 2
3 Figure 14.27: Bonding and anitbonding MOs Figure 14.28: MO energy-level diagram for the H 2 molecule # ANTIBONDING e s es =0 # BONDING e s = 2 Bond order = ½(2-0) = 1 Copyright Houghton Mifflin Company. All rights reserved. 14a 13 Copyright Houghton Mifflin Company. All rights reserved. 14a 14 Figure 14.29: The MO energy-level diagram for the He 2 molecule Figure 14.29: The MO energy-level diagram for the He 2 molecule # ANTIBONDING e s = 2 # BONDING e s = 2 Bond order = ½(2-2) = 0 Copyright Houghton Mifflin Company. All rights reserved. 14a 15 Copyright Houghton Mifflin Company. All rights reserved. 14a 16 Figure 14.30: The MO energy-level diagram for the He 2+ ion. Figure 14.31: The MO energy-level diagram for the H 2+ ion # ANTIBONDING e s = 1 # BONDING e s = 2 Bond order = ½(2-1) = ½ Copyright Houghton Mifflin Company. All rights reserved. 14a 17 Copyright Houghton Mifflin Company. All rights reserved. 14a 18 3
4 Figure 14.32: The MO energy-level diagram for the H 2- ion Copyright Houghton Mifflin Company. All rights reserved. 14a 19 Copyright Houghton Mifflin Company. All rights reserved. 14a 20 Figure 14.33: The relative sizes of the lithium 1s and 2s atomic orbitals Figure 14.34: The MO energy-level diagram for the Li 2 molecule Copyright Houghton Mifflin Company. All rights reserved. 14a 21 Copyright Houghton Mifflin Company. All rights reserved. 14a 22 Figure 14.35: The three mutually perpendicular 2p orbitals on tow adjacent boron atoms. Figure 14.37: The expected MO energy-level diagram for the combustion of the 2 P orbitals on two boron atoms. Copyright Houghton Mifflin Company. All rights reserved. 14a 23 Copyright Houghton Mifflin Company. All rights reserved. 14a 24 4
5 Figure 14.36: The two p oribitals on the boron atom that overlap head-on combine to form bonding and antibonding orbitals. Figure 14.36: The two p oribitals on the boron atom that overlap head-on combine to form bonding and antibonding orbitals. Copyright Houghton Mifflin Company. All rights reserved. 14a 25 Copyright Houghton Mifflin Company. All rights reserved. 14a 26 Figure 14.37: The expected MO energy-level diagram for the combustion of the 2 P orbitals on two boron atoms. Figure 14.37: The expected MO energy-level diagram for the combustion of the 2 P orbitals on two boron atoms. Copyright Houghton Mifflin Company. All rights reserved. 14a 27 Copyright Houghton Mifflin Company. All rights reserved. 14a 28 Figure 14.37: The expected MO energy-level diagram for the combustion of the 2 P orbitals on two boron atoms. Figure 14.38: The expected MO energy-level diagram for the B 2 molecule Copyright Houghton Mifflin Company. All rights reserved. 14a 29 Copyright Houghton Mifflin Company. All rights reserved. 14a 30 5
6 Figure 14.39: An apparatus used to measure the paramagnetism of a sample Figure 14.40: The correct MO energy-level diagram for the B 2 molecule. Copyright Houghton Mifflin Company. All rights reserved. 14a 31 Copyright Houghton Mifflin Company. All rights reserved. 14a 32 Figure 14.41: The MO energy-level diagrams, bond orders, bond energies, and bond lengths for the diatomic molecules, B 2 through F 2. Figure 14.42: When liquid oxygen is poured into the space between the poles of a strong magnet, it remains there until it boils away. Source: Donald Clegg Copyright Houghton Mifflin Company. All rights reserved. 14a 33 Copyright Houghton Mifflin Company. All rights reserved. 14a 34 Figure 14.43: The MO energy-level diagram for the NO molecule Figure 14.44: The MO energy-level diagram for both the NO+ and CN- ions Copyright Houghton Mifflin Company. All rights reserved. 14a 35 Copyright Houghton Mifflin Company. All rights reserved. 14a 36 6
![(frequency) = speed [m/s] Energy Per](/docs-images/77/75878577/images/7-9.jpg "photon: E = h ν λν = c [10 8 m/s]")
7 Figure 14.45: A partial MO energy-level diagram for the HF molecule Figure 14.46: The electron probability distribution in the bonding MO of the HF molecule Copyright Houghton Mifflin Company. All rights reserved. 14a 37 Copyright Houghton Mifflin Company. All rights reserved. 14a 38 Spectroscopy Electromagnetic spectrum Copyright Houghton Mifflin Company. All rights reserved. 14a 39 Copyright Houghton Mifflin Company. All rights reserved. 14a 40 (wavelength) x (frequency) = speed [m/s] Energy Per photon: E = h ν λν = c [10 8 m/s] Copyright Houghton Mifflin Company. All rights reserved. 14a 42 7
8 Electromagnetic spectrum WHAT MAKES A MOLECULE ABSORB LIGHT? When should you push? AT THE RESONANT FREQUENCY ν λ Copyright Houghton Mifflin Company. All rights reserved. 14a 43 Copyright Houghton Mifflin Company. All rights reserved. 14a 44 AT THE RESONANT FREQUENCY λν=c Figure 14.55: The molecular orbital diagram for the ground state of NO + 14 * Electronic transitions: ~ 6 x 10 sec. 500 nm (UV-VIS) Copyright Houghton Mifflin Company. All rights reserved. 14a 45 Copyright Houghton Mifflin Company. All rights reserved. 14a 46 AT THE RESONANT FREQUENCY λν=c 14 * Electronic transitions: ~ 6 x 10 sec. 500 nm (UV-VIS) 13 * Nuclear vibration: ~ 3 x 10 sec. 10,000 nm ( IR) * molecular rotation: microwaves Copyright Houghton Mifflin Company. All rights reserved. 14a 47 Copyright Houghton Mifflin Company. All rights reserved. 14a 48 8
9 What makes a molecule absorb light? Figure 14.60: The three fundamental vibrations for sulfur dioxide [cm -1 ] = 1/λ = ν/c =E/hc Copyright Houghton Mifflin Company. All rights reserved. 14a 50 What makes a molecule absorb light? 3200 cm 1 broad, strong O-H stretch (alcohols) 3000 cm 1 broad, medium O-H stretch (carboxylic acids) 1200 cm 1 strong, O-H bending 2800 cm 1 strong, C-H stretch 1400 cm 11 variable, C-H bending 1700 cm 1 strong, C=O stretch 1200 cm 1 strong, C-O stretch Copyright Houghton Mifflin Company. All rights reserved. 14a 51 What makes a molecule absorb light? Figure 14.61: The infrared spectrum of CH 2 Cl 2. Copyright Houghton Mifflin Company. All rights reserved. 14a 54 9
10 What makes a molecule absorb light? Figure 14.52: Schematic representation of two electronic energy levels in a molecule Copyright Houghton Mifflin Company. All rights reserved. 14a 56 Figure 14.53: The various types of transitions are shown by vertical arrows. Figure 14.54: Spectrum corresponding to the changes indicated in Fig Copyright Houghton Mifflin Company. All rights reserved. 14a 57 Copyright Houghton Mifflin Company. All rights reserved. 14a 58 The molecular structure of beta-carotene Figure 14.57: The electronic absorption spectrum of beta-carotene. Copyright Houghton Mifflin Company. All rights reserved. 14a 59 Copyright Houghton Mifflin Company. All rights reserved. 14a 60 10
11 VIBRATIONS VIBRATIONS Figure 14.58: The potential curve for a diatomic molecule Figure 14.59: Morse energy curve for a diatomic molecule. Copyright Houghton Mifflin Company. All rights reserved. 14a 63 Copyright Houghton Mifflin Company. All rights reserved. 14a 64 Figure 14.62: Representations of the two spin states of the proton interacting Figure 14.63: The molecular structure of bromoethane Copyright Houghton Mifflin Company. All rights reserved. 14a 65 Copyright Houghton Mifflin Company. All rights reserved. 14a 66 11
12 Figure 14.64: The expected NMR spectrum for bromoethane Figure 14.65: The spin of proton H y can by "up" or "down" Copyright Houghton Mifflin Company. All rights reserved. 14a 67 Copyright Houghton Mifflin Company. All rights reserved. 14a 68 Figure 14.66: The spins for protons H y can be "up", can be opposed (in 2 ways) or can both be "down" Figure 14.67: The spins for the protons H y can by arranged as shown in (a) leading to four different magnetic environments Copyright Houghton Mifflin Company. All rights reserved. 14a 69 Copyright Houghton Mifflin Company. All rights reserved. 14a 70 Figure 14.68: The NMR spectrum of CH 3 CH 2 B r (bromoethane) with TMS reference Figure 14.69: The molecule (2-butanone) Copyright Houghton Mifflin Company. All rights reserved. 14a 71 Copyright Houghton Mifflin Company. All rights reserved. 14a 72 12
13 Figure 14.70: A technician speaks to a patient before heis moved intot eh cavity of a magnetic resonance imaging (MRI) machine. Figure 14.71: A colored Magnetic Resonance Imaging (MRI) scan through a human head, showing a healthy brain in side view. Copyright Houghton Mifflin Company. All rights reserved. 14a 73 Copyright Houghton Mifflin Company. All rights reserved. 14a 74 13
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