Absorbance (a.u.) Energy (wavenumber)

Transcription

1

2

3 Absorbance (a.u.) Energy (wavenumber)

4 Animate the Normal Modes of PF 5

5 Selection Rule for Raman Spectroscopy The Raman selection rule is based upon changes in molecular polarizability during a vibration The molecular polarizability may undergo a change during a molecular vibration If the vibration or normal mode has the same symmetry as xz, yz, xy, x 2, y 2, or z 2 then it involves a change in the molecular quadrupole moment during the vibration, by symmetry, and otherwise not There is a mutual exclusion rule for point groups having an inversion center: no vibration may be both IR and Raman active

6 Selection Rule for Raman Spectroscopy The Raman selection rule is based upon changes in molecular polarizability during a vibration The molecular polarizability may undergo a change during a molecular vibration If the vibration or normal mode has the same symmetry as xz, yz, xy, x 2, y 2, or z 2 then it involves a change in the molecular quadrupole moment during the vibration, by symmetry, and otherwise not There is a mutual exclusion rule for point groups having an inversion center: no vibration may be both IR and Raman active

7 Selection Rule for Raman Spectroscopy The Raman selection rule is based upon changes in molecular polarizability during a vibration The molecular polarizability may undergo a change during a molecular vibration If the vibration or normal mode has the same symmetry as xz, yz, xy, x 2, y 2, or z 2 then it involves a change in the molecular quadrupole moment during the vibration, by symmetry, and otherwise not There is a mutual exclusion rule for point groups having an inversion center: no vibration may be both IR and Raman active

8 Selection Rule for Raman Spectroscopy The Raman selection rule is based upon changes in molecular polarizability during a vibration The molecular polarizability may undergo a change during a molecular vibration If the vibration or normal mode has the same symmetry as xz, yz, xy, x 2, y 2, or z 2 then it involves a change in the molecular quadrupole moment during the vibration, by symmetry, and otherwise not There is a mutual exclusion rule for point groups having an inversion center: no vibration may be both IR and Raman active

9 D 6h Illustrates the Rule of Mutual Exclusion

10 Raman is a Light Scattering Phenomenon

11 AsP 3 Characterization by Raman Spectroscopy Intensity (a.u.) cm cm cm Raman Shift (cm -1 ) Raman Shift (cm -1 )

12

13 Using REDUCE for Vibrational Analysis The program only needs to know the # unshifted atoms for each class of operation

14 Using REDUCE for Vibrational Analysis The program only needs to know the # unshifted atoms for each class of operation

15 Using REDUCE for Vibrational Analysis The program only needs to know the # unshifted atoms for each class of operation

16

17 Significance of the 19 F NMR Spectrum of PF 5 Excerpt from 1960 paper by R. Stephen Berry

18 Significance of the 19 F NMR Spectrum of PF 5 Excerpt from 1960 paper by R. Stephen Berry Definition of the term fluxional process: a low-energy, reversible rearrangement

19 Significance of the 19 F NMR Spectrum of PF 5 Excerpt from 1960 paper by R. Stephen Berry Definition of the term fluxional process: a low-energy, reversible rearrangement

20 Significance of the 19 F NMR Spectrum of PF 5 Excerpt from 1960 paper by R. Stephen Berry

21

22 The NMR Time Scale Excerpt from 1983 paper by Robert G. Bryant, DOI: /ed060p933

23 The NMR Time Scale Excerpt from 1983 paper by Robert G. Bryant, DOI: /ed060p933

24 Berry Pseudorotation Cass et al. J. Chem. Educ., 2006, 83, 336 An INTERMEDIATE is at a local minimum on the free energy surface A TRANSITION STATE is at a local maximum

25 Berry Pseudorotation Cass et al. J. Chem. Educ., 2006, 83, 336 An INTERMEDIATE is at a local minimum on the free energy surface A TRANSITION STATE is at a local maximum

26 Berry Pseudorotation Cass et al. J. Chem. Educ., 2006, 83, 336 An INTERMEDIATE is at a local minimum on the free energy surface A TRANSITION STATE is at a local maximum

27 Features of the Pseudorotation The point group of PF 5 is D 3h before and after the pseudorotation BPR involves pairwise exchange of axial and equatorial fluorines The transition state (TS) has C 4v symmetry A true TS has one negative root representing an imaginary frequency Animation of this normal mode provides a movie of the reaction coordinate

28 Features of the Pseudorotation The point group of PF 5 is D 3h before and after the pseudorotation BPR involves pairwise exchange of axial and equatorial fluorines The transition state (TS) has C 4v symmetry A true TS has one negative root representing an imaginary frequency Animation of this normal mode provides a movie of the reaction coordinate

29 Features of the Pseudorotation The point group of PF 5 is D 3h before and after the pseudorotation BPR involves pairwise exchange of axial and equatorial fluorines The transition state (TS) has C 4v symmetry A true TS has one negative root representing an imaginary frequency Animation of this normal mode provides a movie of the reaction coordinate

30 Features of the Pseudorotation The point group of PF 5 is D 3h before and after the pseudorotation BPR involves pairwise exchange of axial and equatorial fluorines The transition state (TS) has C 4v symmetry A true TS has one negative root representing an imaginary frequency Animation of this normal mode provides a movie of the reaction coordinate

31 Features of the Pseudorotation The point group of PF 5 is D 3h before and after the pseudorotation BPR involves pairwise exchange of axial and equatorial fluorines The transition state (TS) has C 4v symmetry A true TS has one negative root representing an imaginary frequency Animation of this normal mode provides a movie of the reaction coordinate

32 Molecular Structure of SF 4, Another Fluxional Molecule

33 NMR Investigation of Pseudorotation in SF 4 Excerpt from 1983 paper by Nancy S. True, DOI: /ja00363a003

34 NMR Investigation of Pseudorotation in SF 4 Excerpt from 1983 paper by Nancy S. True, DOI: /ja00363a003

35 Screenshot of our SF 4 TS Vibrations Applet

36 Summary of Some Key Points The reaction coordinate as a 2D slice of the potential energy surface (PES) Intermediates versus Transition States Intermediates are local minima, zero negative vibrational modes Transition state structures are characterized by a single negative vibrational mode Visualizing the imaginary mode of a TS is essentially a movie of the path from reactants to products BPR as an example of a fluxional process

37 Summary of Some Key Points The reaction coordinate as a 2D slice of the potential energy surface (PES) Intermediates versus Transition States Intermediates are local minima, zero negative vibrational modes Transition state structures are characterized by a single negative vibrational mode Visualizing the imaginary mode of a TS is essentially a movie of the path from reactants to products BPR as an example of a fluxional process

38 Summary of Some Key Points The reaction coordinate as a 2D slice of the potential energy surface (PES) Intermediates versus Transition States Intermediates are local minima, zero negative vibrational modes Transition state structures are characterized by a single negative vibrational mode Visualizing the imaginary mode of a TS is essentially a movie of the path from reactants to products BPR as an example of a fluxional process

39 Summary of Some Key Points The reaction coordinate as a 2D slice of the potential energy surface (PES) Intermediates versus Transition States Intermediates are local minima, zero negative vibrational modes Transition state structures are characterized by a single negative vibrational mode Visualizing the imaginary mode of a TS is essentially a movie of the path from reactants to products BPR as an example of a fluxional process

40 Summary of Some Key Points The reaction coordinate as a 2D slice of the potential energy surface (PES) Intermediates versus Transition States Intermediates are local minima, zero negative vibrational modes Transition state structures are characterized by a single negative vibrational mode Visualizing the imaginary mode of a TS is essentially a movie of the path from reactants to products BPR as an example of a fluxional process

41 Summary of Some Key Points The reaction coordinate as a 2D slice of the potential energy surface (PES) Intermediates versus Transition States Intermediates are local minima, zero negative vibrational modes Transition state structures are characterized by a single negative vibrational mode Visualizing the imaginary mode of a TS is essentially a movie of the path from reactants to products BPR as an example of a fluxional process

42 Summary of Some Key Points Symmetry properties informs discussion of structure and vibrational spectra Selection rules for IR and Raman spectroscopy Vibrational analysis, use REDUCE to check your work Time scales vary for different kinds of measurement (NMR versus IR) The power of multinuclear NMR for studying inorganic systems

43 Summary of Some Key Points Symmetry properties informs discussion of structure and vibrational spectra Selection rules for IR and Raman spectroscopy Vibrational analysis, use REDUCE to check your work Time scales vary for different kinds of measurement (NMR versus IR) The power of multinuclear NMR for studying inorganic systems

44 Summary of Some Key Points Symmetry properties informs discussion of structure and vibrational spectra Selection rules for IR and Raman spectroscopy Vibrational analysis, use REDUCE to check your work Time scales vary for different kinds of measurement (NMR versus IR) The power of multinuclear NMR for studying inorganic systems

45 Summary of Some Key Points Symmetry properties informs discussion of structure and vibrational spectra Selection rules for IR and Raman spectroscopy Vibrational analysis, use REDUCE to check your work Time scales vary for different kinds of measurement (NMR versus IR) The power of multinuclear NMR for studying inorganic systems

46 Summary of Some Key Points Symmetry properties informs discussion of structure and vibrational spectra Selection rules for IR and Raman spectroscopy Vibrational analysis, use REDUCE to check your work Time scales vary for different kinds of measurement (NMR versus IR) The power of multinuclear NMR for studying inorganic systems