1. OXIDES OF CARBON CHAINS: RESULTS OBTAINED ON IR AND UV/VIS ABSORPTIONS. Columbus, Ohio, June 22, 2006 D.Strelnikov, R. Reusch and W. Krätschmer Max-Planck-Institut für Kernphysik, Heidelberg, Germany

2. Experimental Setup

3. Carbon vapor molecules as deposited in cryogenic Ne-, Ar- or Kr-matrices Chain growth by matrix annealing UV/Vis-spectra before and after annealing in Ar IR-spectra before and after annealing in Ar Growth of carbon chains in matrices

4. Selective LASER-induced oxidation of carbon chains in O 2 -matrices. LASER Difference in absorption before and after LASER exposure UV/Vis IR

5. IR spectrum of carbon in Ar matrix Absorbance Units Wavenumbers, cm -1 C5C5 C7C7 C9C9 C 10 C8C8 C3C3 C9C9 C 11 C 10 C6C6 C7C7 C 11 C9C9 C4C4 C6C6 C8C8 C 13 C 15 C 19 C 21 C 17 ? Strelnikov, D.; Reusch, R.; Krätschmer, W. JPCA, 109(34), 2005

6. IR of carbon molecules in O 2 and Ar 1200140016001800200022002400 0.0 0.2 0.4 0.6 0.8 1.0 Absorbance Units Wavenumbers, cm -1 Ar-matrix O 2 -matrix C5C5 C7C7 C9C9 C3C3 C9C9 C 11 C6C6 C7C7 C9C9 C4C4 C6C6 C8C8 C 10 C8C8 Oxide Oxides Oxide Ozone C 13 C 15 C 19 C 21 C 17 ?

7. UV/Vis of carbon molecules in O 2 and Ar. 250300350400450500 0.00 0.05 0.10 0.15 0.20 Absorbance Units Wavelength, nm C 11 C 13 C 15 C 17 C9C9 C6C6 Ar-matrix O 2 -matrix

8. Photobleaching of C X -oxide(s) in O 2 -matrix. UV/Vis. 250300350400450500 0.2 0.4 0.6 0.8 1.0 1.2 Absorbance Units Wavelength, nm LASER C 15 Oxide C 17 Oxide Before irradiation @ 397 nm After 140 min of irradiation Difference C 13 C x O y x≈13 CIS (Hyperchem 6)

9. Photobleaching of C X -oxide(s) in O 2 -matrix. IR. 16001800200022002400 -0.2 -0.1 0.0 0.1 0.2 0.3 0.4 0.5 Absorbance Units Wavenumbers, cm -1 C 13 C3C3 CO 2 C3OC3O C5O2C5O2 Oxide C7O2C7O2 CO Oxide Before irradiation @ 397 nm After 140 min of irradiation Difference C x O y x≈13 DFT b3lyp/6-311g(d,p) (Gaussian 98)

10. Isotopic substitution 16 O  18 O can distinguish between monoxides and dioxides. 1760178018001820184018601880 0.05 0.10 0.15 0.20 0.25 0.30 0.35 0.40 Absorbance Units Wavenumbers, cm -1 C n and C n O m in 16 O 2 C n and C n O m in 18 O 2 C n and C n O m in 50% of 16 O 2 + 50% of 18 O 2 Oxide C 13 Oxides C 11

11. Higher energiesWavenumbers Lower energies C n 16 O C n 18 O 16 O 2 -matrix 18 O 2 -matrix 50% of 16 O 2 + 50% of 18 O 2 16 OC n 16 O 16 OC n 18 O 18 OC n 18 O

12. 250300350400450500 1.5 1.6 1.7 1.8 1.9 2.0 2.1 2.2 Photobleaching of C X -oxide in O 2 -matrix. UV/Vis. Absorbance Units Wavelength, nm LASER C 15 Oxide Before irradiation @ 452 nm After 270 min of irradiation Difference C x O y x≈15 CIS (Hyperchem 6)

13. 16001800200022002400 -0.1 0.0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 Absorbance Units Wavenumbers, cm -1 Photobleaching of C X -oxide in O 2 -matrix. IR. C 13 CO 2 C3OC3O C5O2C5O2 Oxide C7O2C7O2 CO Before irradiation @ 452 nm After 270 min of irradiation Difference C6O2C6O2 Oxide C x O 2 x≈15 DFT b3lyp/ 6-311g(d,p) (Gaussian 98)

14. C6O2*C6O2* 250300350400450500 -0.10 -0.05 0.00 0.05 0.10 Absorbance Units Wavelength, nm Difference after 15 min irradiation @ 308nm Difference after 20 min irradiation @ 440nm C6O2C6O2 Production Destruction + h  h  2050210021502200225023002350 0.02 0.06 0.10 0.14 0.18 Absorbance Units Wavenumbers, cm -1 C6O2C6O2 C3OC3O CO 2 Production Destruction Difference after 15 min irradiation @ 308nm Difference after 20 min irradiation @ 440nm IR UV/Vis C6O2C6O2 C3OC3O C3OC3O * To appear in the JPCA

15. Summary 1400 cm -1 16001800200022002400 500 400 300200 nm C6O2C6O2 Oxide of C 11 Oxide(s) of C 13 Oxides of C 15 Oxides of C 17 UV/VIS Oxide of C 9 IR absorption … 9 11 13 15 17 C9C9 C 11 C 13 C 15 ? ? ? ? ?

16. The Team Wolfgang Krätschmer Dmitry Strelnikov Roman Reusch