Photoionization spectroscopy of the In–N2 van der Waals complex

Abstract

Vibronic structure of the cyclopentadienyl radical and its nonrigid van der Waals cluster with nitrogen A vibrationally resolved electronic spectrum is observed for the metal atom van der Waals complex In-N 2 . Two electronic band systems are detected with mass resolved two-color photoionization spectroscopy. A lower energy system is observed slightly to the blue of the In ͑ 2 D← P͒ atomic asymptote. It is characterized by a progression in the In-N 2 stretching mode with a frequency of e Јϭ76.7 cm Ϫ1 . The higher energy system is slightly to the blue of the In ͑ 4 P← 2 P͒ asymptote. It also exhibits a progression in the In-N 2 stretch with a frequency of e Јϭ87.7 cm Ϫ1 . Extrapolation of the vibrational progressions leads to determination of the excited state dissociation energies. Energetic cycles based on the electronic transition energies, excited state dissociation energies, and atomic asymptotes lead to a determination of the ground state dissociation energy of D 0 Љϭ1519 cm Ϫ1 ͑0.188 eV͒. A single-photon photoionization experiment determines the ionization potential to be 43 372 cm Ϫ1 ͑5.377 eV͒. This IP value, together with the atomic IP and the ground state neutral dissociation energy, yields a dissociation energy of D 0 Љϭ4817 cm Ϫ1 ͑0.597 eV͒ for the In ϩ -N 2 ion-molecule complex.

Intrinsic Dinitrogen Activation at Bare Metal Atoms

“…In the case of [InN 2 ] + , a much higher fragmentation energy of 57.6 kJ mol À1 is obtained. [82] 5.1.5. Group 14 CNN can be generated by photolysis of NCN 3 in fluorohydrocarbon matrices.…”

“…The R2PI method has been used to study experimentally the [InN 2 ] + and [InN 2 ] complexes. [82] As anticipated, the results indicate that the bonding in [InN 2 ] + is much stronger than in [InN 2 ]. The (zero-field) ionization threshold of [InN 2 ] was determined to be 43 372 cm À1 (about 518.7 kJ mol À1 ).…”

Intrinsische Stickstoff‐Aktivierung an “nackten” Metallatomen

“…81 Dies ist angesichts der Unterschiede der Dipolmomente und Polarisierbarkeiten von N 2 und NH 3 verständlich. Die R2PI‐Methode wurde für die experimentelle Untersuchung des [InN 2 ] + ‐ und [InN 2 ]‐Komplexes verwendet 82. Die Ergebnisse zeigen, dass die Bindung in [InN 2 ] + erwartungsgemäß viel stärker ist als in [InN 2 ].…”

“…Demnach sind die Wechselwirkungen zwischen In und N 2 mit denen zwischen Ga und N 2 vergleichbar. Im Fall von [InN 2 ] + erhält man mit 57.6 kJ mol −1 eine viel höhere Fragmentierungsenergie 82…”

Experimental observation of TiN12+ cluster and theoretical investigation of its stable and metastable isomers

“…Andrews and co-workers investigated Fe-N 2 , Sc-N 2 , Os-N 2 , and Ru-N 2 complexes with matrix-isolated infrared spectroscopy [12][13][14][15] and found that an Os atom can insert directly into the dinitrogen bond to form bent NOsN. Duncan and coworkers investigated In-N 2 and Al-N 2 complexes by photoionization spectroscopy, 16,17 and studied Mg + -N 2 , Ca + -N 2 , Nb + (N 2 ) n , and V + (N 2 ) n complexes using photodissociation spectroscopy. [18][19][20][21] Dagdigian and co-workers studied the electronic states of an Al-N 2 complex with laser-induced uorescence spectroscopy.…”