Laser-induced fluorescence of CNN in an Ar matrix

Wurfel, Brent E.; Thoma, A.; Schlachta, Richard; Bondybey, V. E.

doi:10.1016/0009-2614(92)86113-v

Cited by 25 publications

(18 citation statements)

References 15 publications

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“…More recent ab initio calculations by Suter et al 18 yielded ground state vibrational frequencies in good agreement with the newer experimental values. 6 Configuration interaction methods were applied to the X 3 ⌺ Ϫ , ã 1 ⌬, Ã 3 ⌸, and 1 ⌸ states, 19 yielding a calculated fluorescence lifetime value for the Ã 3 ⌸ state of 216 ns in good agreement with the reported experimental lifetimes of 220 and 280 ns from matrix LIF emission studies. 11,19 Clifford et al 15 have used ab initio methods to calculate the electron affinity, excited state term energies, and ground state vibrational frequencies for the CNN radical.…”

Section: Introductionmentioning

confidence: 55%

“…The first infrared absorption measurements on CNN revealed transitions at 1241, 393, and 2847 cm Ϫ1 that were assigned to fundamentals 1 (symmetric stretch), 2 (bend), and 3 (asymmetric stretch), respectively. 4,5 More recent Fourier transform/laser-induced fluorescence ͑FT-LIF͒ emission studies in an Ar matrix 6 found the ground state asymmetric stretch ( 3 ) to be 1419 cm Ϫ1 , suggesting that the intensity of the infrared fundamental transition is ''accidentally'' zero and that the transition observed at 2847 cm Ϫ1 in previous work is the 3 overtone. With this new value for the 3 frequency, similar force constants were found for the C-N and N-N bonds, indicating that both are double bonds.…”

Section: Introductionmentioning

confidence: 84%

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Photodissociation dynamics of the CNN free radical

Bise

Hoops

Choi

et al. 2000

The Journal of Chemical Physics

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The spectroscopy and photodissociation dynamics of the Ã 3 ⌸ and B 3 ⌺ Ϫ states of the CNN radical have been investigated by fast beam photofragment translational spectroscopy. Vibronic transitions located more than 1000 cm Ϫ1 above the Ã 3 ⌸←X 3 ⌺ Ϫ origin were found to predissociate. Photofragment yield spectra for the B 3 ⌺ Ϫ ←X 3 ⌺ Ϫ band between 40 800 and 45 460 cm Ϫ1 display resolved vibrational progressions with peak spacing of Ϸ1000 cm Ϫ1 corresponding to symmetric stretch 1 0 n and combination band 1 0 n 3 0 1 progressions. Ground state products C(3 P)ϩN 2 were found to be the major photodissociation channel for both the Ã 3 ⌸ and B 3 ⌺ Ϫ states. The translational energy distributions for the Ã 3 ⌸ state are bimodal with high and low translational energy components. The distributions for the B 3 ⌺ Ϫ state reveal partially resolved vibrational structure for the N 2 photofragment and indicate extensive vibrational and rotational excitation of this fragment. These results suggest that bent geometries are involved in the dissociation mechanism and provide more accurate values: ⌬ f H 0 ͑CNN͒ϭ6.16Ϯ0.05 eV and ⌬ f H 298 ͑CNN͒ϭ6.15Ϯ0.05 eV. These values, coupled with recent D 0 ͑RH͒ and D 298 ͑RH͒ values from Clifford et al. ͓J. Phys. Chem. 102, 7100 ͑1998͔͒, yield ⌬ f H 0 ͑HCNN͒ϭ5.02Ϯ0.18 eV, ⌬ f H 298 ͑HCNN͒ϭ4.98Ϯ0.18 eV, ⌬ f H 0 ͑H 2 CNN͒ϭ3.09Ϯ0.21 eV, and ⌬ f H 0 ͑H 2 CNN͒ϭ3.09Ϯ0.21 eV.

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Section: Introductionmentioning

confidence: 55%

Section: Introductionmentioning

confidence: 84%

Photodissociation dynamics of the CNN free radical

Bise

Hoops

Choi

et al. 2000

The Journal of Chemical Physics

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“…3 AE À ), the symmetric and antisymmetric C À N stretching modes occur at 1235 and 1419 cm À1 , respectively, and the bending mode at 396 cm À1 . [84] A force constant of 860 N m À1 is thereby derived for both NÀN and CÀN stretching, together with a force constant of 30 N m À1 for C-N-N bending. These values argue for the presence of C À N and N À N double bonds in the molecule (contrary to an earlier report [85] ).…”

Section: Group 13mentioning

confidence: 99%

“…CNN is less stable than NCN. [83,84] Co 2 D electronic ground state. Observed in matrix-isolation studies.…”

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confidence: 99%

Intrinsic Dinitrogen Activation at Bare Metal Atoms

Himmel¹,

Reiher²

2006

Angew Chem Int Ed

119

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There is ongoing interest in metal complexes which bind dinitrogen and facilitate either its reduction or oxidation under mild conditions. In nature, the enzyme nitrogenase catalyzes this process, and dinitrogen fixation occurs under mild and ambient conditions at a metal-sulfur cluster in the center of the MoFe protein, but the mechanism of this process remains largely unknown. In the last few years, new important discoveries have been made in this field. In this review are discussed recent findings on the interaction of N(2) with metal atoms and metal-atom dimers from all groups of the periodic table as provided by gas-phase as well as matrix-isolation experiments. Intrinsic dinitrogen activation at such bare metal atoms is then related to corresponding processes at complexes, clusters, and surfaces.

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“…Messungen der laserinduzierten Fluoreszenz ( 3 Π→ 3 ∑ − ) zufolge liegen die symmetrische und die antisymmetrische C‐N‐Schwingungsmode bei 1235 bzw. 1419 cm −1 und die Biegeschwingung bei 396 cm −1 84. Man erhält daraus 860 N m −1 für die N‐N‐ wie für die C‐N‐Valenzkraftkonstante und 30 N m −1 für die C‐N‐N‐Winkeldeformationskraftkonstante.…”

Section: Distickstoff‐fixierung Durch Ligandenfreie Metallatomeunclassified

Intrinsische Stickstoff‐Aktivierung an “nackten” Metallatomen

Himmel

Reiher

2006

Angewandte Chemie

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Das Interesse an Metallkomplexen, die molekularen Stickstoff binden und seine Reduktion oder Oxidation unter milden Bedingungen bewirken, ist weiterhin ungebrochen. In der Natur katalysiert das Enzym Nitrogenase diesen Prozess. Unter milden Zellbedingungen findet die Distickstoff‐Fixierung an einem Metall‐Schwefel‐Cluster im Zentrum des MoFe‐Proteins statt. Details des Mechanismus sind jedoch weithin unbekannt, obwohl gerade in den letzten Jahren wichtige Entdeckungen in diesem Gebiet gemacht wurden. Im vorliegenden Aufsatz werden neueste Resultate über Wechselwirkungen von N2 mit Metallatomen und Metallatom‐Dimeren aller Gruppen des Periodensystems diskutiert, die vor allem in Gasphasen‐ und Matrixisolationsexperimenten gewonnen wurden. Die Relevanz dieser intrinsischen Distickstoff‐Aktivierung an ligandenfreien Metallatomen für die entsprechenden Reaktionen an Komplexen, Clustern und Oberflächen wird hervorgehoben.

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Laser-induced fluorescence of CNN in an Ar matrix

Cited by 25 publications

References 15 publications

Photodissociation dynamics of the CNN free radical

Photodissociation dynamics of the CNN free radical

Intrinsic Dinitrogen Activation at Bare Metal Atoms

Intrinsische Stickstoff‐Aktivierung an “nackten” Metallatomen

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