The structure and energetics of carbon-nitrogen clusters

DETERMINATION OF IONIZATION ENERGIES OF CnN (n= 4-12): VACUUM ULTRAVIOLET PHOTOIONIZATION EXPERIMENTS AND THEORETICAL CALCULATIONS

“…Specifically, it underestimates the barriers of chemical reactions, the band gaps of materials, the energies of dissociating molecular ions, and charge transfer energies (Cohen et al 2008). On the other hand, DFT optimized geometries show good agreement with MP2, CCSD(T), and experimental results for the related systems of cumulene and polyyne isomers (C 3 H 4 , C 5 H 4 , and C 7 H 4 ) (Woodcock et al 2002), and likewise, for C n N clusters, match well with experiment (Belbruno, et al 2001;Chuchev & BelBruno 2002). Thus the combination of B3LYP/cc-pVTZ optimized geometries and CCSD(T)/cc-pVTZ energies for the present calculations of 218 C n N (n=1-14) species is valid in terms of chemical accuracy and computer efficiency.…”

“…Thus the combination of B3LYP/cc-pVTZ optimized geometries and CCSD(T)/cc-pVTZ energies for the present calculations of 218 C n N (n=1-14) species is valid in terms of chemical accuracy and computer efficiency. Among these 218 species, 15 linear and 12 cyclic species have been investigated in previous theoretical works (Belbruno, et al 2001;Botschwina 1996;Botschwina et al 1997;Chuchev, et al 2002;Ding et al 2001;Green 1980;Maclean, et al 2007;Mebel, et al 2002;Pauzat et al 1991;Resat et al 1994;Wang et al 2009) in which the geometries were obtained almost exclusively by DFT since 2001, with an exception of the relatively small C 3 N + computed by CASSCF. Furthermore, C 4 H 2 and C 6 H 2 are used as test cases where the calculated IEs, 10.06 eV and 9.42 eV, respectively, are of good agreement to the experimental values of 10.17 eV and 9.50 eV, respectively (Bieri et al 1977).…”

“…During the last decades, the spectroscopic (Grutter et al 1999) and thermodynamic properties (Belbruno et al 2001;Golovin & Takhistov 2004) of nitrogen-terminated carbon clusters of the generic formula C n N have received considerable attention due to their role in the astrochemical evolution of the interstellar medium (Fuchs et al 2004;Hasegawa & Herbst 1993;Herbst & Leung 1989) and their contribution to the cosmic carbon budget Eichelberger et al 2007;Redman et al 2003;Ziurys 2006). These radicals are linear in nature, belong to the C ∞v point group, and are considered as building blocks to form hydrogen-deficient polycyclic aromatic hydrocarbon molecules (PAHs) and possibly carbonaceous grain particles in the outflow of carbon stars.…”

Dicyanocarbene and Its Isomers: A Matrix Spectroscopic Study

“…Belbruno et al calculated dicyanocarbene (5) as part of a study on the structures and energetics of a long list of carbon-nitrogen clusters. [19] More closely related to our work is the report of Blanksby, Schwarz et al on a neutralization/reionization mass spectrometric investigation of 5 in the gas phase and calculations on the species involved. [20] The observed scrambling of all three carbon atoms in 13 C-labelled 5 is combined with a theoretical treatment of the mechanism of these rearrangements.…”

Slow photoelectron velocity-map imaging spectroscopy of C2N−, C4N−, and C6N−

“…The C 4 N and C 6 N radicals have been studied experimentally by microwave spectroscopy 25 and theoretically using density functional theory ͑DFT͒. [26][27][28] The only experimental information on C 2n N − anions comes from mass spectrometry studies in which the anions were produced by laser ablation 29,30 or sputtering. 31 Both experiments yielded strong even-odd alternations with the C 2n N − ions being considerably less intense than the C 2n+1 N − ions.…”