The 3Πu ← X 3Δ1g band system of jet-cooled Ti2

Abstract

A band of jet-cooled 48Ti2 has been located in the near infrared by resonant two-photon ionization spectroscopy. Rotational analysis has shown the band to be an Ω′=0±←Ω″=1 transition, which is consistent with the 3Δg ground state proposed by Bauschlicher et al. [J. Chem. Phys. 95, 1057 (1991)]. The band is assigned as a 3Π0u ← X 3Δ1g transition, and lower and upper state bond lengths have been determined as r0(X 3Δg)=1.9422±0.0008 Å and r0(3Πu)=1.997±0.009 Å (1σ error limits, corrected for spin–uncoupling effects). Comparisons are made to the TiV and V2 molecules, a rationale for the unusual filling order of the 3d-based molecular orbitals is provided, and molecular orbital assignments are considered for the excited 3Πu state.

Electronic and geometric structures of Co2Cn− and V2Cn−: Initial growth mechanisms of late and early 3d transition-metal carbide clusters

“…The bond lengths of M 2 are summarized in Table I. [33][34][35][36] The calculations agree fairly well with the experiments with a difference of only 0.04 Å at most. One exception was Mn 2 , where the present calculation predicted the spin multiplicity of 11, while the singlet ground state is reported for matrix-isolated Mn 2 by the electron-spin-resonance experiment.…”

Geometries, stabilities, and electronic properties of small GanTi(0,±1) (n=1–10) clusters studied by density functional theory

“…The bond length R e = 2.837 Å and vibrational frequency x e = 150.51 cm À1 of Ga 2 are obtained, which are in agreement with other theoretical calculations [22] and in reasonable agreement with the scarce experimental data (x e = 165 cm À1 ) [20]. As for Ti 2 dimer, the experimental bond length, vibrational frequency, dissociation energy, and ionization potentials are 1.942 Å [38], 407.9 cm À1 [39], 1.40 eV [40] , and 4.9976IP66.125 eV [38], respectively. The other theoretical bond length, vibrational frequency, dissociation energy, and ionization potentials are 1.89 Å [41], 470 cm À1 [41], 1.22 eV [42], and 5.96 eV [41], respectively.…”

Ti2: Accurate Determination of the Dissociation Energy from Matrix Resonance Raman Spectra and Chemical Interaction With Noble Gases

“…In Figure 8 the experimentally derived G(u) and u data points are fitted by using Equation (2). It can be seen that the fitted curve runs through all observed data points.…”

“…2) The band splitting is completely absent in the case of Ti 2 in Kr and much larger for Ti 2 in Xe. 3) Most convincingly, the degree of splitting of the two components in an Ar matrix is affected by small quantities (2 %) of Xe in the matrix.…”

“…Consensus seems now to be reached with respect to the question of the ground state of Ti 2 , which is in all certainty 3 D g . [1] , [2] However, the energy differences between this ground state and three electronic states (e.g., 1 S þ g , 3 …”