1. LASER-INDUCED FLUORESCENCE STUDIES OF THE JET-COOLED CARBON DIOXIDE AND NITROUS OXIDE CATIONS June. 2010 Mohammed A. Gharaibeh and Dennis J. Clouthier Department of Chemistry, University of Kentucky, Lexington, KY 40506-0055

2. Introduction Astronomical importance: the emission bands of CO 2 + have been found in the Martian dayglow and aurora, and in the tails of comets. Play a role in the operation of high power carbon dioxide lasers. CO 2 Plays an important role in the ionosphere, as it is the intermediate in the reaction of O + and N 2. N2O+N2O+ +

3. L  S  Spin orbit coupling and Renner-Teller effect in triatomic 2  systems uu A   3/2   1/2  2  1/2 2  5/2 2  3/2  2  1/2 2121 uu A

4. CO 2 MO diagram +     uu gg SHOMO HOMO

5. Splitting of the degenerate levels ( 2  ) A=0,  =0 A  0,  0 2  1/2 2  3/2  2  1/2 2  5/2 2  3/2  2  1/2  2  3/2  2  7/2  2  5/2  2  1/2 2  1/2 2  3/2  2  3/2  2  1/2 2  1/2 2  3/2 V”=0 2121 2 1 V’=0 A2A2 X2X2 l =1 l =0,2 2S+1 K P K=| ±  ± l | P=| ±  ± l |=| ±  ±  ± l | Selection Rules:  K=  = 0  P=0 ~ ~

6. Production of jet-cooled cations Pulsed valve Ring electrodes Reheat tube Vacuum (~10 -5 torr) 50 psi of 5% CO 2 in Ar CO 2 + 40 psi of 10% N2O in Ar N2O+N2O+ HV

7. Wavenumber (cm -1 ) Low resolution LIF spectrum of 12 CO 2 2  3/2 2  1/2 2  3/2 2  1/2 X 2  A 2  ~ ~ + 1

8. Q(1.5) Q(0.5) A 2  3/2 ← X 2  3/2 A 2  1/2 ←X 2  1/2 Rotationally-resolved spectrum Experimental Simulated ~ ~ ~ ~

9. Single vibronic level emission spectra of 13 CO 2 Displacement (cm -1 ) Selection Rules:  K=  = 0  P=0 +

10. Parameter A 2  12 COA 2  13 COX 2  13 CO  1 1122.41(19)1121.61(25)1265.6(12)  2 466.75(14)452.32(18)499.70(75)  3 2653.07(36)2580.38(22)…  -0.0924(2)-0.0925(4)-0.1878(8) A -94.69(29)-95.25(34)-161.28(35) W 1 21.294(53)19.64(15)26.69(34) g k 1.89(25)1.23(29)…    2.02(50)1.23(34)… x 11 -3.594(30)-3.329(44)-9.59(36) x 13 -19.04(36)-17.15(13)… N 424027 RMS 0.620.711.9 ~ ~ ~ + 2 + 2 + 2 Vibronic parameters (cm −1 ) for the A 2  and X 2  states of 12 CO 2 and 13 CO 2 + + ~ ~

11. Parameter A 2  12 COA 2  13 CO  1 1122.41(19)1121.61(25)  2 466.75(14)452.32(18)  3 2653.07(36)2580.38(22)  -0.0924(2)-0.0925(4) A -94.69(29)-95.25(34) ~ ~ + 2 + 2 Checking the validity of the results Teller–Redlich product rule

12.        N 2 O + MO diagram SHOMO HOMO

13. Potential-energy curves of N 2 O + Energy R (N-NO + ) X 2  u ~ AA ~    (NO + +N) B 2  u ~

14. 0 2121 3131 2 Wavenumber(cm -1 ) Low resolution LIF spectrum of N 2 O + A2A2 X 2   X 2   ~ ~ ~

15. A=0,  =0 A  0,  0 X2X2 2S+1 K P  2  1/2 2  5/2 2  3/2  2  1/2  2  3/2  2  7/2  2  5/2  2  1/2 2  1/2 2  3/2  2  3/2  2  1/2 2  1/2 2  3/2 2121 2 1 V”=0 2121 2 1 V’=0 l =0,2 l =1 A2A2  2  2  2  l =0,2 l =1 ~ ~ Renner-Teller Analysis ( 2  ) K=| ±  ± l | P=| ±  ± l |=| ±  ±  ± l | Selection Rules:  K=  = 0

16. 3n3n 3n113n11 1234 012 0 Displacement (cm -1 ) N 2 O + Emission spectrum A2A2 X 2   X 2   ~ ~ ~

17. ParameterCurrent work Theory* 11 1142.09(64) 1141.0 22 452.76(40) 412.8 (496.5) 33 1762.0(13) 1778.7 A -132.43(54) -132.367  -0.1693(10) -0.183 W1W1 9.25(41) N48 RMS1.53 Vibronic parameters (in cm -1 ) for the X 2  state of N 2 O + * H. Gritli, Z. Benlakhdar, G. Chambaud, and P. Rosmus, Chemical Physics 178 (1-3), 223 (1993). ~

18. Summary 1- Low resolution LIF spectra have been obtained for A 2  state of 12 CO 2 + and 13 CO 2 + and the A 2  state of N 2 O +. 2- Emission spectra has been obtained from several vibronic levels of the A 2  state of 13 CO 2 + and the A 2  state of N 2 O +. 3- Vibronic energy levels of the A 2  state of 12 CO 2 + and 13 CO 2 +, X 2  state of 13 CO 2 + and the X 2  state of N 2 O + have been satisfactorily fitted to a Renner–Teller model including spin-orbit and Fermi resonance. ~ ~ ~ ~ ~ ~ ~