Electronic spectra are observed for the monosolvated metal cation complexes Ca+–H2O and Ca+–D2O using resonance enhanced photodissociation spectroscopy. The clusters are produced in a laser vaporization/supersonic expansion source and the mass-analyzed product is observed using a time-of-flight mass spectrometer. Both Ca+ and CaOH+ (or CaOD+) dissociation channels are observed on sharp resonances. Transitions from the ground electronic state to two excited electronic states are assigned, with vibrational progressions in the Ca–OH2 stretching mode. Spectroscopic constants are Ca+–H2O: (2) 2B2←X 2A1 (T0=21 464 cm−1, ΔG1/2=357.9 cm−1) and (2) 2B1←X 2A1 (T0=23 273 cm−1, ΔG1/2=335.9 cm−1); and Ca+–D2O: (2) 2B2←X 2A1 (T0=21 447 cm−1, ΔG1/2=350.9 cm−1) and (2) 2B1←X 2A1 (T0=23 261 cm−1, ΔG1/2=324.1 cm−1). These transitions are rotationally resolved, confirming the structure of the complex to be C2v. The Ca+–H2O bond distance is 2.22 Å and the H–O–H bond angle is 106.8° in the ground state. Comparisons with theoretical calculations are also made.
A comparative study of the hyperfine interactions in the X 2Σ+ state of TiN and the X 3Δ state of TiO has been performed. The 48Ti14N(I=1) hyperfine structure was determined from the analysis of 19 components of the N=1–0 and N=2–1 pure rotational transitions recorded using the pump/probe microwave-optical double resonance technique. The 47Ti(I=5/2) hyperfine structure of X 2Σ+ TiN was determined from an analysis of the high resolution optical spectrum of the (0,0) A 2Π3/2–X 2Σ+ band system. The resulting parameters are (in MHz) B(48Ti14N)=18 589.3513(13), D(48Ti14N)=0.026 31(18), γ(48Ti14N)=−52.2070(13), bF(N)=18.480(3), c(N)=0.166(7), eQq0(N)=−1.514(8), CI(N)=0.0137(12), bF(47Ti) =−558.8(11), c(47Ti)=−15(5), and eQq0(47Ti)=62(16). An analysis of the (0,0) band of the B 3Π–X 3Δ system of 47Ti16O produced the X 3Δ hyperfine parameters (in MHz): a(47Ti) =−54.7(21), (bF+2c/3)(47Ti)=−231.6(60), and eQq0(47Ti)=−49(31). An interpretation based upon the predicted nature of the bonding in TiO and TiN is given.
The permanent electric dipole moments of CaOH and SrOH in their X 2Σ+, A 2Π3/2, A 2Π1/2, and B 2Σ+ states have been measured using the technique of supersonic molecular beam optical Stark spectroscopy. For CaOH the values obtained were μ(X 2Σ+)=1.465(61)D, μ(A 2Π1/2)=0.836(32)D, μ(A 2Π3/2)=0.766(24)D, and μ(B 2Σ+)=0.744(84)D, while for SrOH the values were μ(X 2Σ+)=1.900(14)D, μ(A 2Π1/2)=0.590(45)D, μ(A 2Π3/2)=0.424(5)D, and μ(B 2Σ+)=0.396(61)D. The results are compared with values from a recent ab initio calculation for CaOH and with the predictions of a semiempirical electrostatic polarization model.
Electronic spectra are observed for the metal cation complex Ca+–CO2, using resonance-enhanced photodissociation spectroscopy. The complexes are produced in a laser vaporization/supersonic expansion source, size selected and excited on resonance, and the mass-analyzed product is measured in a time-of-flight mass spectrometer. Both Ca+ and CaO+ dissociation channels are observed to have sharp resonances. Spectra from two isotopomers, the 40Ca+ and 44Ca+ species, are recorded and analyzed. Transitions from the X 2Σ+(v″=0) ground vibronic state to several vibrational levels in the D 2Πr excited electronic state are measured. The structure of the complex is confirmed to be linear by the presence of prominent spin–orbit multiplets. Spectroscopic constants for the 40Ca+–CO2 complex are determined: ν00=22 099.1 cm−1, Aso′=136.3 cm−1, ωe′=258.9 cm−1, and ωexe′=4.23 cm−1.
scite is a Brooklyn-based organization that helps researchers better discover and understand research articles through Smart Citations–citations that display the context of the citation and describe whether the article provides supporting or contrasting evidence. scite is used by students and researchers from around the world and is funded in part by the National Science Foundation and the National Institute on Drug Abuse of the National Institutes of Health.