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.

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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

Experimental Setup

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

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

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

IR of carbon molecules in O 2 and Ar 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 ?

UV/Vis of carbon molecules in O 2 and Ar Absorbance Units Wavelength, nm C 11 C 13 C 15 C 17 C9C9 C6C6 Ar-matrix O 2 -matrix

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

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

Isotopic substitution 16 O  18 O can distinguish between monoxides and dioxides 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 % of 18 O 2 Oxide C 13 Oxides C 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 % of 18 O 2 16 OC n 16 O 16 OC n 18 O 18 OC n 18 O

Photobleaching of C X -oxide in O 2 -matrix. UV/Vis. Absorbance Units Wavelength, nm LASER C 15 Oxide Before 452 nm After 270 min of irradiation Difference C x O y x≈15 CIS (Hyperchem 6)

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 452 nm After 270 min of irradiation Difference C6O2C6O2 Oxide C x O 2 x≈15 DFT b3lyp/ 6-311g(d,p) (Gaussian 98)

C6O2*C6O2* Absorbance Units Wavelength, nm Difference after 15 min 308nm Difference after 20 min 440nm C6O2C6O2 Production Destruction + h  h  Absorbance Units Wavenumbers, cm -1 C6O2C6O2 C3OC3O CO 2 Production Destruction Difference after 15 min 308nm Difference after 20 min 440nm IR UV/Vis C6O2C6O2 C3OC3O C3OC3O * To appear in the JPCA

Summary 1400 cm 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 … C9C9 C 11 C 13 C 15 ? ? ? ? ?

The Team Wolfgang Krätschmer Dmitry Strelnikov Roman Reusch