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  • 1
    Electronic Resource
    Electronic Resource
    Molecular-beam laser spectroscopy of lanthanum monofluoride: Magnetic hyperfine and dipole moment measurements (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 97 (1992), S. 4669-4678 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The lanthanum monofluoride molecule (LaF) was generated in a pulsed molecular beam by chemical reaction in a laser-produced plasma. The (0,0) and (1,0) bands of the B 1Π–X 1Σ+ system of LaF (ν00=16 184.52 cm−1), and the 0+–X 1Σ+ band (ν00=16 637.95 cm−1), were investigated at sub-Doppler resolution (120 MHz) using a ring dye laser to excite fluorescence. The electron orbital-nuclear spin interaction parameter (magnetic hyperfine a parameter) was determined to be +138(5) MHz and +149(5) MHz for the v=0 and v=1 levels of the B 1Π state, respectively (2σ error bounds). The observed hyperfine structure is interpreted in terms of ligand field theory. Molecular rotational constants for all three bands were found to be in good agreement with previous work [Schall et al., J. Mol. Spectrosc. 100, 437 (1983)]. The permanent electric dipole moments of the X 1Σ+ and 0+ states of LaF were determined by molecular-beam Stark spectroscopy to be 1.808(21) D and 3.43(10) D (2σ errors). Results are compared with recent experimental determinations of the dipole moments of the other group III monofluorides.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.463952
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  • 2
    Electronic Resource
    Electronic Resource
    Molecular beam Stark spectroscopy of the C 1Σ+–X 1Σ+ (0,0) band of yttrium monochloride (1992)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 96 (1992), S. 2565-2572 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The yttrium monochloride molecule (YCl) has been produced in a free jet molecular beam apparatus by chemical reaction in a laser-produced plasma. The origin band of the C 1Σ+–X 1Σ+ system of YCl was probed at the sub-Doppler resolution of 120 MHz using a ring dye laser to excite fluorescence. Spectra due to the two isotopomers 89Y35Cl and 89Y37Cl were obtained, and molecular constants determined. The following bond lengths were derived (89Y35Cl):r0(X)=2.384 78(36) A(ring), r0(C)=2.460 50(40) A(ring) (2σ error bounds). Results for the ground state are in good agreement with those recently reported by Xin et al. [J. Mol. Spectrosc. 148, 59 (1991)]. The permanent electric dipole moments for both the X and C states were determined by performing molecular beam Stark spectroscopy on the lines P(1) and R(0), respectively. Values of 2.587(29) D (X state) and 3.258(36) D (C state) were obtained. Results are compared with ab initio predictions of the molecular parameters, and a molecular orbital interpretation of the bonding is presented.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.462845
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  • 3
    Electronic Resource
    Electronic Resource
    Spectroscopy of the indium argon van der Waals complex: A high resolution study of the B 2Σ1/2←X2 2Π3/2 system (1993)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 4300-4311 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The InAr van der Waals complex has been characterized by high resolution laser induced fluorescence excitation spectroscopy. Six vibronic bands of the B 2Σ1/2←X2 2Π3/2 transition have been observed and five of these (v',0), where v'=1–5, have been rotationally analyzed. Rydberg–Klein–Rees potential curves were constructed for the B 2Σ1/2 state using the rotational and vibrational constants determined from these spectra. Equilibrium bond lengths were determined for the B and X2 states and a dissociation energy was determined for the B state. The stronger bonding present in the B state is rationalized in terms of penetration of the argon atom into the diffuse 6s orbital of indium. Evidence is presented that the B state potential energy curve has a barrier at long range, due to Pauli repulsion, of ∼60 cm−1. An analysis of the hyperfine structure involving the 115In nucleus was made. It is concluded that the X2 state conforms to Hund's coupling case aβ, whereas the B state conforms to case bβs. The extent of 6s–6p hybridization in the upper state was measured from hyperfine splittings and was used in conjunction with a simple electrostatic model to estimate the polarizability of the indium atom in the 6s 2S1/2 state. A value of 68(4) A(ring)3 was obtained (1σ error).
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.466083
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  • 4
    Electronic Resource
    Electronic Resource
    Electronic spectroscopy of the niobium dimer molecule: Experimental and theoretical results (1993)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 99 (1993), S. 8504-8518 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Rotationally resolved electronic spectra of the niobium dimer molecule are reported for the first time. The molecules were produced by laser vaporization of a niobium target rod and cooled in a helium supersonic expansion. The molecular beam containing niobium dimer molecules was interrogated in the range 400–900 nm using a pulsed dye laser to excite fluorescence. Numerous Ω=0←Ω=0 and Ω=1←Ω=1 vibronic transitions were discovered in the region 630–720 nm and investigated at 200 MHz resolution using the cw output of a single mode ring dye laser. The principal features were classified into five Ω=0←Ω=0 systems originating from a common lower state of 0+g symmetry, and three Ω=1←Ω=1 systems originating from a common lower state of 1g symmetry. The two lower states were assigned as the Ω=0 and Ω=1 spin–orbit components of the X 3Σ−g ground state, which is derived from the electron configuration 1π4u1σ2g2σ2g1δ2g. The two spin–orbit components are split by several hundred cm−1 due to a strong, second-order isoconfigurational spin–orbit interaction with the low-lying 1Σ+g state. Evidence for significant 4d orbital participation in the Nb2 bond is furnished by the short bondlength [re=2.077 81(18) A(ring)] and large vibrational frequency [ωe=424.8917(12) cm−1] determined for the X 3Σ−g(0+g) state (2σ error bounds). The electronic structure of niobium dimer was investigated using density functional theory. For the electronic ground state, the predicted spectroscopic properties were in good agreement with experiment. Calculations on excited states reveal congested manifolds of triplet and singlet electronic states in the range 0–3 eV, reflecting the multitude of possible electronic promotions among the 4d- and 5s-based molecular orbitals. The difficulties of correlating the experimentally observed electronic transitions with specific valence electronic promotions are addressed. Comparisons are drawn between Nb2 and the isoelectronic molecule V2.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.465627
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  • 5
    Electronic Resource
    Electronic Resource
    Optical laser Stark spectroscopy of the yttrium monosulfide molecule (1993)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 98 (1993), S. 4422-4428 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The yttrium monosulfide molecule was produced in a pulsed molecular beam apparatus by chemical reaction in a laser-generated plasma. The permanent electric dipole moments of the X 2Σ+ and B 2Σ+ states were determined by molecular beam Stark spectroscopy to be 6.098(64) D and 4.572(92) D, respectively (2σ error bounds). Results are interpreted in terms of a molecular orbital description of the bonding. The experimental data are compared with dipole moment measurements for related molecules, and with the predictions of ab initio theory.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.465002
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  • 6
    Electronic Resource
    Electronic Resource
    Pulsed field ionization zero kinetic energy photoelectron spectroscopy of the vanadium dimer molecule (1995)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 102 (1995), S. 3129-3134 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: The technique of pulsed-field-ionization zero-kinetic-energy (PFI-ZEKE), photoelectron spectroscopy was employed to probe the electronic structure of the V+2 cation. Rotationally resolved PFI-ZEKE spectra of the V+2 ground state were obtained by two color excitation via the 700 nm A 3Πu←X 3Σ−g system. The observation of transitions from the A 3Π2u state to two spin–orbit components with Ω=1/2 and Ω=3/2, confirms that the cation ground state has 4Σg− symmetry, in accordance with previous experimental and theoretical work. Striking differences were observed in the rotational selection rules for the 4Σg−←A 3Π1u and the 4Σg−←A 3Π2u transitions. The adiabatic ionization potential of V2 was determined to be 51 271.14(50) cm−1. From an analysis of the rotational structure of the PFI-ZEKE spectra, the following molecular constants were determined for the 4Σg− state: r0=1.7347(24) A(ring), second order spin–orbit splitting, λ=5.248(17) cm−1, spin–rotation constant, γ=0.0097(87) cm−1, T0=51 282.20(50) cm−1 (1σ error bounds). © 1995 American Institute of Physics.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.468623
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  • 7
    Electronic Resource
    Electronic Resource
    Resonant two photon ionization spectroscopy of the molecules V2, VNb, and Nb2 (1994)
    College Park, Md. : American Institute of Physics (AIP)
    The Journal of Chemical Physics 101 (1994), S. 4485-4495 
    Details
    ISSN: 1089-7690
    Source: AIP Digital Archive
    Topics: Physics , Chemistry and Pharmacology
    Notes: Resonant two photon ionization (R2PI) spectroscopy was used to obtain detailed spectroscopic information on the neutral and cation ground states of the jet-cooled molecules V2, VNb, and Nb2. By recording photoionization efficiency (PIE) spectra, their adiabatic ionization potentials were determined to be 51 269(5) cm−1 (V2), 51 554(10) cm−1 (VNb), and 51 359(10) cm−1 (Nb2). In VNb, we used different ionization routes to determine that the splitting between the Ω=0 and Ω=1 spin–orbit components of the X 3Σ− ground state was 230(3) cm−1. In the case of V2 and VNb, two thresholds were observed in the PIE spectra recorded via Ω=1 intermediate states. We were thus able to assign the ground states of V+2 and VNb+ as having 4Σ− symmetry, with second-order spin–orbit splittings of 20(3) and 82(3) cm−1, respectively. A simple model was applied to calculate the locations of the 1Σ+ and 2Σ+ states which are responsible for the second-order spin–orbit splitting of the neutral and cation ground states, respectively. One-color R2PI spectroscopy was employed to determine the bond dissociation energy of VNb, the result D00=30 562(10) cm−1 being obtained. The implications of our measurements regarding the relative bond strengths of the neutral and cationic dimers are discussed.
    Type of Medium: Electronic Resource
    URL: http://dx.doi.org/10.1063/1.468462
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