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
24 - Rotationally resolved spectroscopy of Mg+–rare gas complexes
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: ion–molecule complexes; photodissociation spectroscopy; Hund's coupling cases; rotational structure in open-shell molecules; least-squares fitting of spectra.
This Case Study follows on from the previous one. However, rotationally resolved photodissociation spectra are the focus here, specifically for Mg+–Ne and Mg+–Ar. Although these ions are diatomic species, their rotationally resolved spectra are not trivial to analyse. The reason for this is the presence of an unpaired electron, which gives rise to a net spin angular momentum which can interact with the overall rotation of the complex (spin–rotation coupling). In addition, in some electronic states there may also be a net orbital angular momentum, and this can interact both directly with the molecular rotation (giving rise to the phenomenon known as Λ doubling) and with the electron spin. The latter is much the strongest of these angular momentum interactions and its effect can be readily seen in the rotationally resolved spectra, as will be discussed below.
Duncan and co-workers have recorded partly rotationally resolved electronic spectra for the A2Π˗ X2Σ+ transitions of Mg+–Ne and Mg+–Ar, and these form the basis of the Case Study described here [1, 2]. A photodissociation technique was employed as detailed in Chapter 23. Before describing the spectra and their analysis, the expected rotational energy level structure for the X2Σ+ and A2Π electronic states is considered. Much of this description is similar to that met for NO in Chapter 22.
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- Information
- Electronic and Photoelectron SpectroscopyFundamentals and Case Studies, pp. 197 - 204Publisher: Cambridge University PressPrint publication year: 2005