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Molecular Orbitals An approach to bonding in which orbitals encompass the entire molecule, rather than being localized bet...
Molecular Orbitals <ul><li>Molecular orbitals result from the combination of atomic orbitals.  </li></ul><ul><li>Since orb...
Molecular Orbitals <ul><li>Molecular orbitals form when atomic orbitals with similar energies and proper symmetry can over...
Need for MO Theory <ul><li>Valence bond theory fails to explain the bonding in many simple molecules.  </li></ul><ul><li>T...
Need for MO Theory <ul><li>Valence bond theory predicts the double bond, but not the paramagnetism of oxygen. </li></ul><u...
Need for MO Theory <ul><li>Resonance is another example of the limitations of valence bond theory.  Bond lengths and stren...
Molecular Orbital Theory <ul><li>In order to simplify things, we’ll consider the interaction of the orbitals containing va...
Molecular Orbital Theory <ul><li>Constructively: </li></ul><ul><li>Ψ ( σ )  or  Ψ +  = ( 1/√2 )  [ φ (1s a )  +  φ (1s b )...
Molecular Orbital Theory <ul><li>The bonding orbital results in increased electron density between the two nuclei, and is ...
Molecular Orbital Theory <ul><li>The antibonding orbital results in a node between the two nuclei, and is of greater energ...
Molecular Orbital Theory <ul><li>The result is an energy level diagram with the bonding orbital occupied by a pair of elec...
Molecular Orbital Theory <ul><li>The bonding orbital is sometimes given the notation  σ g , where the  g  stands for  gera...
Molecular Orbital Theory <ul><li>The anti-bonding orbital is sometimes given the notation  σ u , where the  u  stands for ...
Rules for Combining Atomic Orbitals <ul><li>The number of molecular orbitals = the  number of atomic orbitals combined. </...
Experimental Evidence <ul><li>Photoelectron spectroscopy (PES) is a technique in which a beam of ultraviolet light with an...
Experimental Evidence <ul><li>The technique allows for the measurement of specific ionization energies (I).  Each ionizati...
Experimental Evidence <ul><li>Electrons in lower energy levels require more energy to be removed, and are ejected with les...
Period 2 Diatomic Molecules <ul><li>For the second period, assume that, due to a better energy match,  s  orbitals combine...
MOs using  p  orbitals <ul><li>With the  x  axis as the bond axis, the p x  orbitals may combine constructively or destruc...
MOs using  p  orbitals <ul><li>The designation  σ  indicates symmetric electron density around the internuclear ( x ) axis...
MOs using  p  orbitals <ul><li>Some texts will use the symmetry designations of  g  (gerade) or  u  (ungerade) instead of ...
MOs using  p  orbitals <ul><li>For these orbitals, the bonding orbital is  gerade , or symmetric around the bond axis. </l...
MOs using  p  orbitals <ul><li>For these orbitals, the anti-bonding orbital is asymmetric about the bond axis, and is desi...
π  Molecular Orbitals <ul><li>The orbital overlap side-by-side is less than that of overlap along the bond axis (end-on-en...
π  Molecular Orbitals <ul><li>π  orbitals are asymmetric with respect to the bond axis.  There is electron density surroun...
π  Molecular Orbitals <ul><li>Some texts use the subscripts  g  and  u  instead of bonding and anti-bonding.  In this exam...
π  Molecular Orbitals <ul><li>The anti-bonding orbital is  gerade , or symmetric about a center of symmetry. </li></ul>sid...
Molecular Orbital Diagram <ul><li>This is a molecular orbital energy level diagram for the  p  orbitals.  Note that the  σ...
Molecular Orbital Diagram <ul><li>The alternate notation is provided on the right side of the energy level diagram. </li><...
Molecular Orbital Diagrams <ul><li>Electrons preferentially occupy molecular orbitals that are lower in energy. </li></ul>...
Molecular Orbital Diagrams <ul><li>Although molecular orbitals form from inner (core) electrons as well as valence electro...
Molecular Orbital Diagrams <ul><li>For O 2 , there will be a total of 12 valence electrons that must be placed in the diag...
Molecular Orbital Diagrams <ul><li>For O 2 , there will be a total of 12 valence electrons that must be placed in the diag...
Molecular Orbital Diagrams <ul><li>For O 2 , there will be a total of 12 valence electrons that must be placed in the diag...
MO Diagram for O 2 2p 2p 2s 2s σ g σ * u σ g π u π * g σ * u The molecular orbital diagram for oxygen shows two unpaired e...
Bond Order <ul><li>Bond order is an indicator of the bond strength and length.  A bond order of 1 is equivalent to a singl...
MO Diagram for O 2 2p 2p 2s 2s σ g σ * u σ g π u π * g σ * u The bond order of O 2  is: 8-4  = 2   2 This is consistent wi...
MO Diagram for O 2 2p 2p 2s 2s σ g σ * u σ g π u π * g σ * u This energy level diagram works well for atoms in which the 2...
Experimental Evidence <ul><li>Oxygen is paramagnetic, consistent with having two unpaired electrons.  In addition,  photoe...
Photoelectron Spectroscopy <ul><li>The result is a spectrum of absorptions which are correlated to the molecular orbitals ...
Muhammad Asif Pakistan
MO diagram for Li through N <ul><li>The elements on the left side of period 2 have a fairly small energy gap between the 2...
MO diagram for Li through N <ul><li>In some approaches, the s orbital on one atom interacts with the p orbital on another....
MO diagram for Li through N <ul><li>In another approach, the s and p orbitals on the  same  atom interact in what is calle...
MO diagram for Li through N σ g σ g σ * u σ * u π u π * g Muhammad Asif Pakistan
MO diagram for N 2 N 2  has 10 valence electrons. Muhammad Asif Pakistan σ g σ g σ * u σ * u π u π * g
Experimental Evidence <ul><li>The photoelectronic spectrum of nitrogen is consistent with a molecular orbital approach.  <...
Experimental Evidence Muhammad Asif Pakistan σ g π u σ * u σ g σ g σ * u σ * u π u π * g
Heteronuclear Diatomic  Molecules <ul><li>The more electronegative atom will have orbitals of lower energy, and therefore ...
Rules for Combining Atomic Orbitals <ul><li>For heteronuclear molecules: </li></ul><ul><li>1.  The bonding orbital(s) will...
HF <ul><li>The 2s and 2p x  orbitals on fluorine interact with the 1s orbital on hydrogen.  </li></ul><ul><li>The p y  and...
HF <ul><li>The anti-bonding orbital resides primarily on the less electronegative atom (H). </li></ul><ul><li>Note that th...
Carbon monoxide <ul><li>In carbon monoxide, the bonding orbitals reside more on the oxygen atom, and the anti-bonding orbi...
Carbon monoxide <ul><li>CO is a highly reactive molecule with transition metals.  Reactivity typically arises from the  h ...
Carbon monoxide <ul><li>When acting as an electron pair acceptor, the  l owest  u noccupied  m olecular  o rbital (LUMO), ...
Carbon monoxide <ul><li>When acting as an electron pair donor, the  h ighest  o ccupied  m olecular  o rbital (HOMO), is s...
The highest occupied molecular orbital of CO is a molecular orbital which puts significant electron density on the carbon ...
The lowest unoccupied molecular orbital of CO is the  π * orbitals. The lobes of the LUMO are larger on the carbon atom th...
CO as a Ligand <ul><li>Carbon monoxide is known as a  σ  donor and a  π  acceptor ligand.  It donates electrons from its H...
CO as a Ligand <ul><li>Carbon monoxide accepts electrons from filled  d  orbitals on the metal into its antibonding (LUMO)...
CO as a Ligand <ul><li>This phenomenon is called  back bonding .  The increased electron density in the antibonding orbita...
MOs for Larger Molecules <ul><li>Group theory is usually used to develop molecular orbital diagrams and drawings of more c...
MOs for Larger Molecules <ul><li>The orbitals of the non-central atoms are called  group orbitals .  In considering a simp...
<ul><li>The characters for the group orbitals is obtained by considering each hydrogen as a spherical  1s  orbital.  They ...
Group Orbitals of Water <ul><li>Γ red  and its irreducible representations are: </li></ul>Muhammad Asif Pakistan
Group Orbitals of Water <ul><li>The A 1  representation has both  1s  orbitals with positive wave functions: H a +H b . </...
Group Orbitals of Water <ul><li>These group orbitals are combined with orbitals on oxygen that have the same symmetry. </l...
Group Orbitals of Water The  2s  and  2p z  orbital on oxygen have A 1  symmetry, the  2p x   orbital has B 1  symmetry, a...
Molecular Orbitals of Water <ul><li>Since the  2p y  orbital on oxygen doesn’t match the symmetry of the group orbitals of...
Muhammad Asif Pakistan
MOs for Larger Molecules <ul><li>Group theory is usually used to develop molecular orbital diagrams and drawings of more c...
π  Bonding of Benzene <ul><li>Benzene belongs to point group D 6h .  In determining the orbital combinations for  π  bondi...
π  Bonding of Benzene { z axis C′ 2 C″ 2 Muhammad Asif Pakistan D 6h E 2C 6 2C 3 C 2 3C′ 2 3C″ 2 i 2S 3 2S 6 σ h 3  σ d 3 ...
π  Bonding of Benzene { z axis C′ 2 C″ 2 Muhammad Asif Pakistan D 6h E 2C 6 2C 3 C 2 3C′ 2 3C″ 2 i 2S 3 2S 6 σ h 3  σ d 3 ...
π  Bonding of Benzene { z axis C′ 2 C″ 2 This reduces to:  B 2g  + E 1g  + A 2u  + E 2u Muhammad Asif Pakistan D 6h E 2C 6...
π  Bonding of Benzene <ul><li>Г π :  B 2g  + E 1g  + A 2u  + E 2u </li></ul><ul><li>Group theory can be used to draw each ...
π  Bonding of Benzene <ul><li>Г π :  B 2g  + E 1g  + A 2u  + E 2u </li></ul>A 2u  fully bonding and lowest in energy E 1g ...
π  Bonding of Benzene <ul><li>Г π :  B 2g  + E 1g  + A 2u  + E 2u </li></ul>E 2u  degenerate largely anti-bonding orbitals...
π  Bonding of Benzene Muhammad Asif Pakistan A 2u E 1g E 2u B 2g
Molecular Orbitals of Complexes <ul><li>Group theory is also used to construct molecular orbital diagrams for the complexe...
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Molecular orbitals

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Transcript of "Molecular orbitals"

  1. 1. Molecular Orbitals An approach to bonding in which orbitals encompass the entire molecule, rather than being localized between atoms. Muhammad Asif Pakistan
  2. 2. Molecular Orbitals <ul><li>Molecular orbitals result from the combination of atomic orbitals. </li></ul><ul><li>Since orbitals are wave functions, they can combine either constructively (forming a bonding molecular orbital), or destructively (forming an antibonding molecular orbital). </li></ul>Muhammad Asif Pakistan
  3. 3. Molecular Orbitals <ul><li>Molecular orbitals form when atomic orbitals with similar energies and proper symmetry can overlap. </li></ul><ul><li>Atomic orbitals with differing energies or the wrong spatial orientation (orthogonal) do not combine, and are called non-bonding orbitals. </li></ul>Muhammad Asif Pakistan
  4. 4. Need for MO Theory <ul><li>Valence bond theory fails to explain the bonding in many simple molecules. </li></ul><ul><li>The oxygen molecule has a bond length and strength consistent with a double bond, and it contains two unpaired electrons. </li></ul>Muhammad Asif Pakistan
  5. 5. Need for MO Theory <ul><li>Valence bond theory predicts the double bond, but not the paramagnetism of oxygen. </li></ul><ul><li>O=O </li></ul>: : : : Muhammad Asif Pakistan
  6. 6. Need for MO Theory <ul><li>Resonance is another example of the limitations of valence bond theory. Bond lengths and strengths are intermediate between single, double or triple bonds. </li></ul><ul><li>Molecular orbital theory is often a better approach to use with molecules that have extended π systems. </li></ul>Muhammad Asif Pakistan
  7. 7. Molecular Orbital Theory <ul><li>In order to simplify things, we’ll consider the interaction of the orbitals containing valence electrons to create molecular orbitals. </li></ul><ul><li>The wave functions of hydrogen atom A and hydrogen atom B can interact either constructively or destructively. </li></ul>Muhammad Asif Pakistan
  8. 8. Molecular Orbital Theory <ul><li>Constructively: </li></ul><ul><li>Ψ ( σ ) or Ψ + = ( 1/√2 ) [ φ (1s a ) + φ (1s b ) ] </li></ul><ul><li>Destructively: </li></ul><ul><li>Ψ ( σ *) or Ψ - = ( 1/√2 ) [ φ (1s a ) - φ (1s b ) ] </li></ul>Muhammad Asif Pakistan
  9. 9. Molecular Orbital Theory <ul><li>The bonding orbital results in increased electron density between the two nuclei, and is of lower energy than the two separate atomic orbitals. </li></ul>Muhammad Asif Pakistan
  10. 10. Molecular Orbital Theory <ul><li>The antibonding orbital results in a node between the two nuclei, and is of greater energy than the two separate atomic orbitals. </li></ul>Muhammad Asif Pakistan
  11. 11. Molecular Orbital Theory <ul><li>The result is an energy level diagram with the bonding orbital occupied by a pair of electrons. The filling of the lower molecular orbital indicates that the molecule is stable compared to the two individual atoms. </li></ul>Muhammad Asif Pakistan
  12. 12. Molecular Orbital Theory <ul><li>The bonding orbital is sometimes given the notation σ g , where the g stands for gerade , or symmetric with respect to a center of inversion. </li></ul>+ + - The signs on the molecular orbitals indicate the sign of the wave function, not ionic charge. Muhammad Asif Pakistan
  13. 13. Molecular Orbital Theory <ul><li>The anti-bonding orbital is sometimes given the notation σ u , where the u stands for ungerade , or asymmetric with respect to a center of inversion. </li></ul>+ + - The signs on the molecular orbitals indicate the sign of the wave function, not ionic charge. Muhammad Asif Pakistan
  14. 14. Rules for Combining Atomic Orbitals <ul><li>The number of molecular orbitals = the number of atomic orbitals combined. </li></ul><ul><li>The strength of the bond depends upon the degree of orbital overlap. </li></ul>Muhammad Asif Pakistan
  15. 15. Experimental Evidence <ul><li>Photoelectron spectroscopy (PES) is a technique in which a beam of ultraviolet light with an energy of 21 eV is used to irradiate molecules. </li></ul><ul><li>The energy is high enough to eject electrons. The kinetic energy of the emitted electrons is measured, and used to determine the energy level of the electron. </li></ul>Muhammad Asif Pakistan
  16. 16. Experimental Evidence <ul><li>The technique allows for the measurement of specific ionization energies (I). Each ionization energy represents the removal of an electron from a specific molecular orbital. </li></ul>Muhammad Asif Pakistan
  17. 17. Experimental Evidence <ul><li>Electrons in lower energy levels require more energy to be removed, and are ejected with less kinetic energy. </li></ul><ul><li>h ν o = I + E kinetic </li></ul>Muhammad Asif Pakistan
  18. 18. Period 2 Diatomic Molecules <ul><li>For the second period, assume that, due to a better energy match, s orbitals combine with s orbitals, and p orbitals combine with p orbitals. </li></ul><ul><li>The symmetry of p orbitals permits end-on-end overlap along the bond axis, or side-by-side overlap around, but not along, the internuclear axis. </li></ul>Muhammad Asif Pakistan
  19. 19. MOs using p orbitals <ul><li>With the x axis as the bond axis, the p x orbitals may combine constructively or destructively. The result is a σ bonding orbital and a σ anti-bonding orbital. </li></ul>+ + + - - - - Muhammad Asif Pakistan
  20. 20. MOs using p orbitals <ul><li>The designation σ indicates symmetric electron density around the internuclear ( x ) axis. The + and – signs indicate the sign of the wave function, and not electrical charges. </li></ul>+ + + - - - - Muhammad Asif Pakistan
  21. 21. MOs using p orbitals <ul><li>Some texts will use the symmetry designations of g (gerade) or u (ungerade) instead of indicating bonding or anti-bonding. </li></ul>+ + + - - - - Muhammad Asif Pakistan
  22. 22. MOs using p orbitals <ul><li>For these orbitals, the bonding orbital is gerade , or symmetric around the bond axis. </li></ul>+ + + - - - - σ g Muhammad Asif Pakistan
  23. 23. MOs using p orbitals <ul><li>For these orbitals, the anti-bonding orbital is asymmetric about the bond axis, and is designated as σ u . Note that the designations of u or g do not correlate with bonding or anti-bonding. </li></ul>+ + + - - - - σ g σ u Muhammad Asif Pakistan
  24. 24. π Molecular Orbitals <ul><li>The orbital overlap side-by-side is less than that of overlap along the bond axis (end-on-end). As a result, the bonding orbital will be higher in energy than the previous example. </li></ul>side-by-side overlap + + + - - - Muhammad Asif Pakistan
  25. 25. π Molecular Orbitals <ul><li>π orbitals are asymmetric with respect to the bond axis. There is electron density surrounding the bond axis, with a node along the internuclear axis. </li></ul>side-by-side overlap + + + - - - Muhammad Asif Pakistan
  26. 26. π Molecular Orbitals <ul><li>Some texts use the subscripts g and u instead of bonding and anti-bonding. In this example, the bonding orbital is ungerade, or asymmetric about a center of symmetry. </li></ul>side-by-side overlap + + + - - - π u Muhammad Asif Pakistan
  27. 27. π Molecular Orbitals <ul><li>The anti-bonding orbital is gerade , or symmetric about a center of symmetry. </li></ul>side-by-side overlap + + + - - - π u π g Muhammad Asif Pakistan
  28. 28. Molecular Orbital Diagram <ul><li>This is a molecular orbital energy level diagram for the p orbitals. Note that the σ bonding orbital is lowest in energy due to the greater overlap end-on-end. </li></ul>2p 2p σ g π u π g σ u Muhammad Asif Pakistan
  29. 29. Molecular Orbital Diagram <ul><li>The alternate notation is provided on the right side of the energy level diagram. </li></ul>2p 2p σ g π u π g σ u Muhammad Asif Pakistan
  30. 30. Molecular Orbital Diagrams <ul><li>Electrons preferentially occupy molecular orbitals that are lower in energy. </li></ul><ul><li>Molecular orbitals may be empty, or contain one or two electrons. </li></ul><ul><li>If two electrons occupy the same molecular orbital, they must be spin paired. </li></ul><ul><li>When occupying degenerate molecular orbitals, electrons occupy separate orbitals with parallel spins before pairing. </li></ul>Muhammad Asif Pakistan
  31. 31. Molecular Orbital Diagrams <ul><li>Although molecular orbitals form from inner (core) electrons as well as valence electrons, many molecular orbital diagrams include only the valence level. </li></ul>Muhammad Asif Pakistan
  32. 32. Molecular Orbital Diagrams <ul><li>For O 2 , there will be a total of 12 valence electrons that must be placed in the diagram. </li></ul>Muhammad Asif Pakistan
  33. 33. Molecular Orbital Diagrams <ul><li>For O 2 , there will be a total of 12 valence electrons that must be placed in the diagram. </li></ul>Muhammad Asif Pakistan
  34. 34. Molecular Orbital Diagrams <ul><li>For O 2 , there will be a total of 12 valence electrons that must be placed in the diagram. </li></ul>2p 2p 2s 2s Muhammad Asif Pakistan
  35. 35. MO Diagram for O 2 2p 2p 2s 2s σ g σ * u σ g π u π * g σ * u The molecular orbital diagram for oxygen shows two unpaired electrons, consistent with experimental data. Muhammad Asif Pakistan
  36. 36. Bond Order <ul><li>Bond order is an indicator of the bond strength and length. A bond order of 1 is equivalent to a single bond. Fractional bond orders are possible. </li></ul><ul><li>The bond order of the molecule = </li></ul><ul><li>(# e - in bonding orbtls) - (# e - in anti-bonding orbtls) </li></ul><ul><li>2 2 </li></ul>Muhammad Asif Pakistan
  37. 37. MO Diagram for O 2 2p 2p 2s 2s σ g σ * u σ g π u π * g σ * u The bond order of O 2 is: 8-4 = 2 2 This is consistent with a double bond. Muhammad Asif Pakistan
  38. 38. MO Diagram for O 2 2p 2p 2s 2s σ g σ * u σ g π u π * g σ * u This energy level diagram works well for atoms in which the 2s and 2p levels are fairly far apart. These are the elements at the right of the table: O, F and Ne. Muhammad Asif Pakistan
  39. 39. Experimental Evidence <ul><li>Oxygen is paramagnetic, consistent with having two unpaired electrons. In addition, photoelectron spectroscopy (PES) can be used for determining orbital energies in molecules. The molecule is bombarded with UV or X-rays to remove an electron from the molecule. The kinetic energy of the emitted electron is measured and subtracted from the incident radiation to determine the binding energy of the electron. </li></ul>Muhammad Asif Pakistan
  40. 40. Photoelectron Spectroscopy <ul><li>The result is a spectrum of absorptions which are correlated to the molecular orbitals of the molecule. In addition, electrons ejected from bonding orbitals show more vibrational energy levels than electrons emitted from anti-bonding or non-bonding orbitals. </li></ul>Muhammad Asif Pakistan
  41. 41. Muhammad Asif Pakistan
  42. 42. MO diagram for Li through N <ul><li>The elements on the left side of period 2 have a fairly small energy gap between the 2s and 2p orbitals. As a result, interaction between s and p orbitals is possible. This can be viewed in different ways. </li></ul>Muhammad Asif Pakistan
  43. 43. MO diagram for Li through N <ul><li>In some approaches, the s orbital on one atom interacts with the p orbital on another. The interaction can be constructive or destructive. </li></ul>Muhammad Asif Pakistan
  44. 44. MO diagram for Li through N <ul><li>In another approach, the s and p orbitals on the same atom interact in what is called orbital mixing . </li></ul><ul><li>Either approach yields the same result. The σ bonding and anti-bonding orbitals are raised in energy due to the interaction with a p orbital. </li></ul>Muhammad Asif Pakistan
  45. 45. MO diagram for Li through N σ g σ g σ * u σ * u π u π * g Muhammad Asif Pakistan
  46. 46. MO diagram for N 2 N 2 has 10 valence electrons. Muhammad Asif Pakistan σ g σ g σ * u σ * u π u π * g
  47. 47. Experimental Evidence <ul><li>The photoelectronic spectrum of nitrogen is consistent with a molecular orbital approach. </li></ul><ul><li>Electrons emitted from bonding orbitals show vibrational excitations. </li></ul>σ g π u σ * u Muhammad Asif Pakistan
  48. 48. Experimental Evidence Muhammad Asif Pakistan σ g π u σ * u σ g σ g σ * u σ * u π u π * g
  49. 49. Heteronuclear Diatomic Molecules <ul><li>The more electronegative atom will have orbitals of lower energy, and therefore contribute more to the bonding orbitals. </li></ul><ul><li>The less electronegative atom has orbitals of higher energy, and contributes more to the anti-bonding orbitals. </li></ul>Muhammad Asif Pakistan
  50. 50. Rules for Combining Atomic Orbitals <ul><li>For heteronuclear molecules: </li></ul><ul><li>1. The bonding orbital(s) will reside predominantly on the atom of lower orbital energy (the more electronegative atom). </li></ul><ul><li>2. The anti-bonding orbital(s) will reside predominantly on the atom with greater orbital energy (the less electronegative atom). </li></ul>Muhammad Asif Pakistan
  51. 51. HF <ul><li>The 2s and 2p x orbitals on fluorine interact with the 1s orbital on hydrogen. </li></ul><ul><li>The p y and p z orbitals on fluorine lack proper symmetry to interact with hydrogen, and remain as non-bonding orbitals. </li></ul>Muhammad Asif Pakistan
  52. 52. HF <ul><li>The anti-bonding orbital resides primarily on the less electronegative atom (H). </li></ul><ul><li>Note that the subscripts g and u are not used, as the molecule no longer has a center of symmetry. </li></ul>Muhammad Asif Pakistan
  53. 53. Carbon monoxide <ul><li>In carbon monoxide, the bonding orbitals reside more on the oxygen atom, and the anti-bonding orbitals reside more on the carbon atom. </li></ul>Muhammad Asif Pakistan
  54. 54. Carbon monoxide <ul><li>CO is a highly reactive molecule with transition metals. Reactivity typically arises from the h ighest o ccupied m olecular o rbital (HOMO), when donating electrons. </li></ul>Muhammad Asif Pakistan
  55. 55. Carbon monoxide <ul><li>When acting as an electron pair acceptor, the l owest u noccupied m olecular o rbital (LUMO), is significant. </li></ul>Muhammad Asif Pakistan
  56. 56. Carbon monoxide <ul><li>When acting as an electron pair donor, the h ighest o ccupied m olecular o rbital (HOMO), is significant. </li></ul>Muhammad Asif Pakistan
  57. 57. The highest occupied molecular orbital of CO is a molecular orbital which puts significant electron density on the carbon atom. Muhammad Asif Pakistan
  58. 58. The lowest unoccupied molecular orbital of CO is the π * orbitals. The lobes of the LUMO are larger on the carbon atom than on the oxygen atom. Muhammad Asif Pakistan
  59. 59. CO as a Ligand <ul><li>Carbon monoxide is known as a σ donor and a π acceptor ligand. It donates electrons from its HOMO to form a sigma bond with the metal. </li></ul>Muhammad Asif Pakistan
  60. 60. CO as a Ligand <ul><li>Carbon monoxide accepts electrons from filled d orbitals on the metal into its antibonding (LUMO) orbital. </li></ul>Muhammad Asif Pakistan
  61. 61. CO as a Ligand <ul><li>This phenomenon is called back bonding . The increased electron density in the antibonding orbitals of CO causes an increase in the C-O bond length and a decrease in its stretching frequency. </li></ul>Muhammad Asif Pakistan
  62. 62. MOs for Larger Molecules <ul><li>Group theory is usually used to develop molecular orbital diagrams and drawings of more complicated molecules. When a central atom is bonded to several atoms of the same element (H 2 O, BF 3 , or PtCl 4 2- ], group theory can be used to analyze the symmetry of the orbitals of the non-central atoms, and then combine them with the appropriate orbitals of the central atom. </li></ul>Muhammad Asif Pakistan
  63. 63. MOs for Larger Molecules <ul><li>The orbitals of the non-central atoms are called group orbitals . In considering a simple example, H 2 O, we obtain group orbitals using the two 1s orbitals on the hydrogen atoms. </li></ul>Muhammad Asif Pakistan
  64. 64. <ul><li>The characters for the group orbitals is obtained by considering each hydrogen as a spherical 1s orbital. They remain in position for identity, are exchanged during rotation, remain in place for σ xz (the molecular plane), and are exchanged for σ yz . </li></ul>Muhammad Asif Pakistan
  65. 65. Group Orbitals of Water <ul><li>Γ red and its irreducible representations are: </li></ul>Muhammad Asif Pakistan
  66. 66. Group Orbitals of Water <ul><li>The A 1 representation has both 1s orbitals with positive wave functions: H a +H b . </li></ul><ul><li>The B 1 representations is H a +H b . </li></ul>Muhammad Asif Pakistan
  67. 67. Group Orbitals of Water <ul><li>These group orbitals are combined with orbitals on oxygen that have the same symmetry. </li></ul>Muhammad Asif Pakistan
  68. 68. Group Orbitals of Water The 2s and 2p z orbital on oxygen have A 1 symmetry, the 2p x orbital has B 1 symmetry, and the 2p y has B 2 symmetry. Muhammad Asif Pakistan
  69. 69. Molecular Orbitals of Water <ul><li>Since the 2p y orbital on oxygen doesn’t match the symmetry of the group orbitals of hydrogen, it will remain non-bonding. The other orbitals on oxygen will combine with the appropriate group orbitals to form bonding and antibonding molecular orbitals. </li></ul>Muhammad Asif Pakistan
  70. 70. Muhammad Asif Pakistan
  71. 71. MOs for Larger Molecules <ul><li>Group theory is usually used to develop molecular orbital diagrams and drawings of more complicated molecules. A simplified example will be shown for the π bonding of benzene. </li></ul>Muhammad Asif Pakistan
  72. 72. π Bonding of Benzene <ul><li>Benzene belongs to point group D 6h . In determining the orbital combinations for π bonding, we need to obtain Г π by looking only at the p z orbitals on each carbon atom. </li></ul>We need only consider those orbitals on carbon atoms that remain in place for a given symmetry operation. Muhammad Asif Pakistan
  73. 73. π Bonding of Benzene { z axis C′ 2 C″ 2 Muhammad Asif Pakistan D 6h E 2C 6 2C 3 C 2 3C′ 2 3C″ 2 i 2S 3 2S 6 σ h 3 σ d 3 σ v Г π
  74. 74. π Bonding of Benzene { z axis C′ 2 C″ 2 Muhammad Asif Pakistan D 6h E 2C 6 2C 3 C 2 3C′ 2 3C″ 2 i 2S 3 2S 6 σ h 3 σ d 3 σ v Г π 6 0 0 0 -2 0 0 0 0 -6 0 2
  75. 75. π Bonding of Benzene { z axis C′ 2 C″ 2 This reduces to: B 2g + E 1g + A 2u + E 2u Muhammad Asif Pakistan D 6h E 2C 6 2C 3 C 2 3C′ 2 3C″ 2 i 2S 3 2S 6 σ h 3 σ d 3 σ v Г π 6 0 0 0 -2 0 0 0 0 -6 0 2
  76. 76. π Bonding of Benzene <ul><li>Г π : B 2g + E 1g + A 2u + E 2u </li></ul><ul><li>Group theory can be used to draw each of the π molecular orbitals. Molecular orbitals with fewer nodes are lower in energy (more bonding), and those with more nodes are higher in energy (more antibonding). </li></ul>Muhammad Asif Pakistan
  77. 77. π Bonding of Benzene <ul><li>Г π : B 2g + E 1g + A 2u + E 2u </li></ul>A 2u fully bonding and lowest in energy E 1g degenerate bonding orbitals with one node Muhammad Asif Pakistan
  78. 78. π Bonding of Benzene <ul><li>Г π : B 2g + E 1g + A 2u + E 2u </li></ul>E 2u degenerate largely anti-bonding orbitals with two nodes B 2g fully anti-bonding orbital with three nodes Muhammad Asif Pakistan
  79. 79. π Bonding of Benzene Muhammad Asif Pakistan A 2u E 1g E 2u B 2g
  80. 80. Molecular Orbitals of Complexes <ul><li>Group theory is also used to construct molecular orbital diagrams for the complexes of metal atoms or ions. The symmetry combinations of the atomic orbitals on the ligands are determined, and then “matched” with appropriate atomic orbitals on the central metal. Both σ and π bonding between the metal and ligands can be considered. </li></ul>Muhammad Asif Pakistan
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