Book contents
- Frontmatter
- Contents
- Preface
- List of journal abbreviations
- Part I Foundations of electronic and photoelectron spectroscopy
- Part II Experimental techniques
- Part III Case Studies
- 13 Ultraviolet photoelectron spectrum of CO
- 14 Photoelectron spectra of CO2, OCS, and CS2 in a molecular beam
- 15 Photoelectron spectrum of NO–2
- 16 Laser-induced fluorescence spectroscopy of C3: rotational structure in the 300 nm system
- 17 Photoionization spectrum of diphenylamine: an unusual illustration of the Franck–Condon principle
- 18 Vibrational structure in the electronic spectrum of 1,4-benzodioxan: assignment of low frequency modes
- 19 Vibrationally resolved ultraviolet spectroscopy of propynal
- 20 Rotationally resolved laser excitation spectrum of propynal
- 21 ZEKE spectroscopy of Al(H2O) and Al(D2O)
- 22 Rotationally resolved electronic spectroscopy of the NO free radical
- 23 Vibrationally resolved spectroscopy of Mg+–rare gas complexes
- 24 Rotationally resolved spectroscopy of Mg+–rare gas complexes
- 25 Vibronic coupling in benzene
- 26 REMPI spectroscopy of chlorobenzene
- 27 Spectroscopy of the chlorobenzene cation
- 28 Cavity ringdown spectroscopy of the a1Δ ← X3Σ–g transition in O2
- Appendix A Units in spectroscopy
- Appendix B Electronic structure calculations
- Appendix C Coupling of angular momenta: electronic states
- Appendix D The principles of point group symmetry and group theory
- Appendix E More on electronic configurations and electronic states: degenerate orbitals and the Pauli principle
- Appendix F Nuclear spin statistics
- Appendix G Coupling of angular momenta: Hund's coupling cases
- Appendix H Computational simulation and analysis of rotational structure
- Index
- References
17 - Photoionization spectrum of diphenylamine: an unusual illustration of the Franck–Condon principle
Published online by Cambridge University Press: 05 June 2012
- Frontmatter
- Contents
- Preface
- List of journal abbreviations
- Part I Foundations of electronic and photoelectron spectroscopy
- Part II Experimental techniques
- Part III Case Studies
- 13 Ultraviolet photoelectron spectrum of CO
- 14 Photoelectron spectra of CO2, OCS, and CS2 in a molecular beam
- 15 Photoelectron spectrum of NO–2
- 16 Laser-induced fluorescence spectroscopy of C3: rotational structure in the 300 nm system
- 17 Photoionization spectrum of diphenylamine: an unusual illustration of the Franck–Condon principle
- 18 Vibrational structure in the electronic spectrum of 1,4-benzodioxan: assignment of low frequency modes
- 19 Vibrationally resolved ultraviolet spectroscopy of propynal
- 20 Rotationally resolved laser excitation spectrum of propynal
- 21 ZEKE spectroscopy of Al(H2O) and Al(D2O)
- 22 Rotationally resolved electronic spectroscopy of the NO free radical
- 23 Vibrationally resolved spectroscopy of Mg+–rare gas complexes
- 24 Rotationally resolved spectroscopy of Mg+–rare gas complexes
- 25 Vibronic coupling in benzene
- 26 REMPI spectroscopy of chlorobenzene
- 27 Spectroscopy of the chlorobenzene cation
- 28 Cavity ringdown spectroscopy of the a1Δ ← X3Σ–g transition in O2
- Appendix A Units in spectroscopy
- Appendix B Electronic structure calculations
- Appendix C Coupling of angular momenta: electronic states
- Appendix D The principles of point group symmetry and group theory
- Appendix E More on electronic configurations and electronic states: degenerate orbitals and the Pauli principle
- Appendix F Nuclear spin statistics
- Appendix G Coupling of angular momenta: Hund's coupling cases
- Appendix H Computational simulation and analysis of rotational structure
- Index
- References
Summary
Concepts illustrated: MATI spectroscopy; vibrational wavefunctions; Franck–Condon principle and Franck–Condon factors.
The photoionization spectrum of diphenylamine provides an unusual and interesting illustration of the Franck–Condon principle. Diphenylamine (DPA), illustrated in Figure 17.1, is a relatively large molecule to study by gas phase spectroscopy and it might be thought that the vibrational structure in its electronic spectra would be highly congested and difficult to interpret. After all, this is a molecule with 66 vibrational modes! However, it was shown in Section 7.2.3 that only totally symmetric modes generally need to be considered in interpreting electronic spectra. Also, there is the further simplification that not all of the totally symmetric modes need be Franck–Condon active, i.e. will give a significant progression. DPA is an excellent example of this, with the main structure arising from a single vibrational mode.
Before spectra are considered, the experimental procedure, carried out by Boogaarts and co-workers [1], will be outlined. Mass-analysed threshold ionization (MATI) spectroscopy was employed. This technique, which was briefly described in Section 12.6, is essentially the same as ZEKE spectroscopy but employs ion rather than electron detection. It has the advantage over ZEKE spectroscopy in that ions can be separated according to their mass, which in most cases enables the spectral carrier to be determined with confidence. By analogy with ZEKE spectroscopy, a cation ← neutral molecule electronic absorption spectrum is effectively obtained.
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- Electronic and Photoelectron SpectroscopyFundamentals and Case Studies, pp. 144 - 149Publisher: Cambridge University PressPrint publication year: 2005