Formation, characterization, structure and bonding analysis of the metal-carbon bond OM-(η6-C6H6) (M = Sc, Ti) complexes in solid matrix: Infrared spectroscopic and theoretical study

Zhao, Yanying,Zhang, Yuchen,Liu, Xin,Fan, Kexue,Zheng, Xuming

, p. 25 - 30 (2015)

The reactions of ScO and TiO molecules with benzene have been studied in solid argon with infrared absorption spectroscopy combining with theoretical calculations. Laser-evaporation of bulk higher oxide targets prepared the scandium and titanium monoxide

Nonequilibrium product distributions observed in the multiple collision chemiluminescent reaction of Sc with NO2. Perturbations, rapid energy transfer routes and evidence for a low-lying reservoir state

Gole, J. L.,Pace, S. A.

, p. 836 - 850 (1980)

Nitrogen dioxide reacts with scandium to yield the B 2Σ+-X 2Σ+ spectrum ScO.This reaction has been characterized from 10-5 to 1 Torr in order to study relaxation and rapid intramolecular E-E transfer among ScOexcited states.At the lowest pressures, a ground state metal atom interacts with a tenuous atmosphere of oxidant gas (beam-gas configuration).These single collision studies are extended in a controlled manner to higher pressure by entraining the metal atoms in argon and subsequently carrying out the oxidation of this mixture.At all pressures, the measured B 2Σ+ vibrational populations follow a markedly non-Boltzmann distribution.At the lowest pressures, the formation of ScO B 2Σ+ results directly from the reaction Sc+NO2->ScO*+NO.At higher pressures, the B 2Σ+ state is also populated via rapid intramolecular energy transfer from long-lived, weakly emitting reservoir states via the sequence Sc+NO2+Ar->ScO(res)+NO+Ar and ScO(res)+Ar->ScO(B 2Σ+)+Ar.Spin orbit and Coriolis interactions in ScO connect rovibronic levels of B 2Σ+ and low-lying 4Πr or 2Πi reservoir states resulting in the observation of substantial perturbations in B 2Σ+.Collisional energy transfer is particularly efficient for the most strongly perturbed levels of the B 2Σ+ state.This energy transfer is manifest by the apperance of extra band heads representing normally forbiden (small electronic transitionmoment or Franck-Condon factor) reservoir state -ground state transitions which become allowed because of a small admixture of B 2Σ+ character.The relative intensities of the extra and main B 2Σ+-X 2Σ+ transitions are strongly dependent on argon buffer gas pressure.A quantitative description of this dependence gives an estimate for the amount of mixing between the reservoir state and B 2Σ+ and for the rate of energy transfer between these two states.Collisional transfer to ScO B 2Σ+ υ'=3-9 is found to proceed at rates which for certain levels approach 100 times gas kinetic.The effects observed in ScO demonstrate that the excited states of this molecule interact in the presence of a collision partner as if they were large diffuse entities.These effects are not pathological.This behavior may have important implications for the modeling of energy systems as well as the ability to create population inversions requisite for the construction of visible chemical laser systems.

Dufek, V.,Petru, F.,Brozhek, V.

, (1967)

Matrix-isolation fourier transform infrared and theoretical studies of laser-ablated Sc atom reactions with water molecules

Zhang, Luning,Dong, Jian,Zhou, Mingfei

, p. 8882 - 8886 (2000)

Laser-ablated Se atoms have been reacted with water molecules during condensation with argon at 11 K. In agreement with previous thermal atom reactions, absorptions at 1482.6 and 713.0 cm-1 are assigned to the HScOH molecule formed via an inser

Work, D. E.,Eick, H. A.

, p. 413 - 416 (1972)

Trends in the Optical Signatures for Transition-Metal Oxide Carbonyl Complexes. Evaluation of Transition-Metal Carbonyl, M(CO)x, Binding Energies

McQuaid, M. J.,Morris, K.,Gole, J. L.

, p. 5280 - 5285 (2007/10/02)

Transition-metal atoms entrained in argon, helium, and CO are oxidized with ozone (O3) and nitrogen dioxide (NO2) to study the nature of the metal atom complexation with CO.We establish a method for evaluating M-CO binding energies through comparison of the chemiluminescent emission from the oxidation of argon- and CO-entrained transition-metal atoms.These studies have thus far yielded Ebinding(Ti(CO)x) ca. 1.75 eV and Ebinding(NiCO) ca. 1.10 eV, the latter in excellent agreement with previous experimental and theoretical evaluations of the Ni-CO bond energy.We identify the optical signatures for transition-metal oxide carbonyl (MOCO) complexes formed in the oxidation of M(CO) complexes.We outline trends in the nature of the observed metal oxide complex emissions.The current study suggests a method for obtaining the spectra of transition-metal carbonyl (M(CO)x, x=1,2) complexes.