1. High-Resolution Spectroscopy and Analysis of the n3/2n4 Dyad of CF4
Vincent BOUDON
Institut Carnot de Bourgogne – UMR 5209 CNRS-Université de Bourgogne, 9 Av. A. Savary, BP 47870, F DIJON, France
Alexandra DOMANSKAYA
Institute of Physics, Saint Petersbourg University, , SAINT PETERSBOURG, Russia
Christof MAUL
Institut für Physikalische un Theoretische Chemie des Technischen Universität Braunschweig, D BRAUNSCHWEIG, Germany
Robert GEORGES
Institut de Physique de Rennes, UMR 6251 CNRS – Université de Rennes 1, 263 Av. Général Leclerc, F RENNES, France
Justin MITCHELL
Department of Physics, University of Arkansas, FAYETTEVILLE, USA

2. The CF4 molecule
CF4 is a strong greenhouse gas (natural and anthropogenic origin)
Global Warming Potential = 6500 (CO2 = 1), lifetime = 50,000 years
Concentration = 75 pptv, annual increase = 1.6 % 1 2 3 4 A1 E F2
Stretching
Bending
Raman IR
909 cm-1
435 cm-1
1283 cm-1
631 cm-1
Point group Td

3. Contents Experimental details Theory
Simultaneous analysis of line positions
Intensities
Semi-classical study

4. I. Experimental details

5. Data used for the simultaneous fit
Static-cell spectra (Braunschweig and Rennes)
Supersonic expansion jet spectrum (Rennes)
MW data for n3–n3 (M. Takami et al., Mol. Phys. 85, 733–744 (1995))

6. II. Theory

7. Effective tensorial Hamiltonian
Polyad structure P0 P1 P2
Systematic tensorial development
Coupled rovibrational basis
Effective Hamiltonian and vibrational extrapolation

8. Effective Hamiltonian for CF4
Effective Hamiltonian for the Ground State (P0 polyad)
Effective Hamiltonian for the v4 = 1 level (= P1 polyad)
Effective Hamiltonian for v4 = 2 / v3 = 1 (= P2) polyad

9. III. Simultaneous analysis of line positions

10. Fit statistics

11. Overview of the n4 band

12. Detail in the n4 band

13. n4 band : fit residuals for line positions

14. The 2n4 band

15. Overview of the n3 band

16. Jet-cooled spectrum of the n3 band

17. n3/2n4 dyad: fit residuals for line positions

18. IV. Intensities

19. Dipole moment parameters
Fit of the proportionality coefficient between the experimental and simulated spectrum to find the dipole moment derivatives
n4 : use of P and R branches
n3 : R branch only, P branch is perturbed by 2n4
Rough estimation for 2n4

20. V. Semi-classical study

21. Semi-classical energy curves

22. Semi-classical vs. quantum levels
See talk RJ06

23. Spherical Top Data System
The STDS database
Spherical Top Data System
• Molecular parameter database
• Calculation and analysis programs
• XTDS : Java interface
NB : CF4 results included in HITRAN 2008