1. IAMS, Academia Sinica, Taiwan, 台灣 中研院原分所 Course: Molecular Spectroscopy Taiwan International Graduate Program (TIGP) Professor: Wen-Bih Tzeng, Lab: 108, Office: 301 e-mail ： wbt@po.iams.sinica.edu.tw wbt@po.iams.sinica.edu.tw website ： http://www.iams.sinica.edu.tw/lab/wbtzeng/indexa.html http://www.iams.sinica.edu.tw/lab/wbtzeng 3 lectures on electronic spectroscopy of molecules in the gas phase Tuesday 9:10-12:00, 2013/2/19 - 2012/3/5 (Classroom: 311) Suggested books (NTU Chemistry Library): 1. Modern Spectroscopy, 4th ed. by J. Michael Hollas, John Wiley & Sons, 2004. 2. Molecular Spectra and Molecular Structure, G. Herzberg, D. van Nostrand Company, Inc., QC 451.H463v.1 1950.

2. Lecture Planning Date 2013/02/19 (Tue)Introduction Some Important Results in Quantum Mechanics Electromagnetic Radiation and its Interaction with Atoms and Molecules (Chapter 1) 2013/02/26 (Tue)Electromagnetic Radiation and its Interaction with Atoms and Molecules (Chapter 2) Electronic spectroscopy (Chapter 7) 2013/03/05 (Tue)Photoelectron spectroscopy and related spectroscopies (REMPI, ZEKE, MATI spectroscopy)

3. Energy Levels

5. wbt5 Resonant two-photon (R2PI) and mass-analyzed threshold ionization (MATI) processes electronic excitation ionization

6. Preparation of C 6 H 5 NHD and C 6 H 5 ND 2 (Mass 93) (Mass 95) (Mass 94)

7. Preparation of C 6 D 5 NHD and C 6 D 5 ND 2 (Mass 100) (Mass 98) (Mass 99)

8. Relative Intensity Mass / amu TOF spectra of deuterium substituted aniline isotopomers λ = 293.94 nm λ = 292.54 nm λ = 292.48 nm 93 ↔ C 6 H 5 NH 2 + 94 ↔ C 6 H 5 NHD + 98 ↔ C 6 D 5 NH 2 + 99 ↔ C 6 D 5 NHD + 100 ↔ C 6 D 5 ND 2 +

9. One photon energy / cm -1 Relative Intensity (a) C 6 H 5 NH 2 (b) C 6 H 5 NHD (b) C 6 H 5 ND 2 Vibronic spectra of deuterium substituted aniline isotopomers

10. Relative Wavenumber / cm -1 Relative Intensity (a) C 6 D 5 NH 2 (b) C 6 D 5 NHD (c) C 6 D 5 ND 2

11. MATI spectra of deuterium substituted aniline isotopomers Ion Internal Energy / cm -1 Relative Intensity via S 1 0 0 34029 cm -1 34031 cm -1 34038 cm -1 (a) C 6 H 5 NH 2 (b) C 6 H 5 NHD (c) C 6 H 5 ND 2

12. Ion Internal Energy / cm -1 Relative Intensity via S 1 0 0 34193 cm -1 34195 cm -1 34202 cm -1 (a) C 6 D 5 NH 2 (b) C 6 D 5 NHD (c) C 6 D 5 ND 2 MATI spectra of deuterium substituted aniline isotopomers

13. 13 Vibronic spectra of m-, o-, p-fluoroaniline by 1C-R2PI

14. 14 Vibronic spectra of m-, o-, p-fluoroaniline by 1C-R2PI

15. 15 Vibronic spectrum of m- and o-fluoroaniline mixture

16. 16 MATI spectra of m-, o-, p-fluoroaniline m-fluoroaniline NIST: 8.32 － 8.33 eV MATI: 7.9543 ± 0.0006 eV o-fluoroaniline NIST: 8.2 － 8.5 eV MATI: 7.8909 ± 0.0006 eV p-fluoroaniline NIST: 7.9 － 8.2 eV MATI: 7.7543 ± 0.0006 eV

17. 17 Vibronic spectra of m-, o-, p-fluoroanisole m-fluoroanisole has cis and trans rotamers.

18. 18 MATI spectra of m-, o-, p-fluoroanisole trans-m-fluoroanisole NIST: 8.4 － 8.7 eV MATI: 8.4686 ± 0.0006 eV cis-m-fluoroanisole NIST: 8.4 － 8.7 eV MATI: 8.4144 ± 0.0006 eV o-fluoroanisole NIST: － MATI: 8.3508 ± 0.0006 eV p-fluoroanisole NIST: 8.3 － 8.6 eV MATI: 8.2371 ± 0.0006 eV

19. IR and REMPI spectra of guanine Ref: (a) IR: Delabar et al., Spectrochim Acta 34A, 129 (1978). (b) REMPI: de Vries and coworkers, JACS 121, 4896 (1999).

20. Possible structures of guanine (c) (b)(a) Ref: de Vries and coworkers, JCP 115, 4606 (2001).

21. REMPI spectrum of guanine Ref: SC Yang, JL Lin, Lab 108, IAMS

22. REMPI spectrum of guanine Ref: SC Yang, JL Lin, Lab 108, IAMS MP2/6-311G(d,p): a=7H-Keto, 1 kJ/mol b=9H-Keto, 4 kJ/mol c=9H-Enol, 0 kJ/mol

23. REMPI spectrum of guanine Ref: SC Yang, JL Lin, Lab 108, IAMS MP2/6-311G(d,p): a=7H-Keto, 1 kJ/mol b=9H-Keto, 4 kJ/mol c=9H-Enol, 0 kJ/mol