First detection and analysis of an electronic spectrum of vanadium hydride: The D5Π-X5Δ (0,0) band.

The D5Π-X5Δ (0,0) band of vanadium hydride at 654 nm has been recorded by laser excitation spectroscopy and represents the first analyzed spectrum of VH in the gas phase. The molecules were generated using a hollow cathode discharge source, with laser-induced fluorescence detected via the D5Π-A5Π (0,0) transition. All five main (ΔΩ = ΔΛ) subbands were observed as well as several satellite ones, which together create a rather complex and overlapped spectrum covering the region 15 180-15 500 cm-1. The D5Π state displays the effects of three strong local perturbations, which are likely caused by interactions with high vibrational levels of the B5Σ- and c3Σ- states, identified in a previous multiconfigurational self-consistent field study by Koseki et al. [J. Phys. Chem. A 108, 4707 (2004)]. Molecular constants describing the X5Δ, A5Π, and D5Π states were determined in three separate least-squares fits using effective Hamiltonians written in a Hund's case (a) basis. The fine structure of the ground state is found to be consistent with its assignment as a σπ2δ, 5Δ electronic state. The fitted values of its first-order spin-orbit and rotational constants in the ground state are A=36.537815cm-1 and B = 5.7579(13) cm-1, the latter of which yields a bond length of R0=1.72122 Å. This experimental value is in good agreement with previous computational studies of the molecule and fits well within the overall trend of decreasing bond length across the series of 3d transition metal monohydrides.

Au-S Bonding Revealed from the Characterization of Diatomic Gold Sulfide, AuS.

Gold monosulfide, AuS, has been detected and characterized in the gas phase using optical spectroscopy. The symmetries of the ground and low-lying electronic excited states have been determined by application of a synergy of hot and cold laser excitation techniques. The electronic spectra are assigned to progressions in four band systems associated with excitations from the X(2)Πi ((2σ)(2)(2π)(3)) ground state to the A(2)Σ(+) state arising from the (2σ)(1)(2π)(4) configuration and to the a(4)Σ(-), B(2)Σ(-), and C(2)Δi states arising from the (2σ)(2)(2π)(2)(3σ*)(1) configuration. The bond length and dissociation energy of the ground X(2)Πi state are determined to be 2.156(2) Å and 298 ± 2 kJ/mol, respectively. A molecular orbital correlation diagram is used to rationalize the energy ordering of the excited states and the associated harmonic frequencies.

Molecular-beam optical stark and zeeman study of the [17.8]0+-X1Σ+ (0,0) band system of AuF.

The [17.8]0(+)-X(1)Σ(+) (0,0) band of gold monofluoride, AuF, has been recorded at a resolution of 40 MHz both field free and in the presence of a static electric and magnetic field. The observed Stark shifts were analyzed to determine the permanent electric dipole moment, µel, of 2.03 ± 0.05 D and 4.13 ± 0.02 D, for the [17.8]0(+)(v = 0) and X(1)Σ(+)(v = 0) states, respectively. The small magnetic tuning observed for the [17.8]0(+)(v = 0) state is attributed to rotational and magnetic field mixing with the [17.7]1 state and has been successfully modeled using an effective Hamiltonian for the (3)Π state. A comparison with the numerous published theoretical predictions is made.

Excited electronic states of AuF.

We have recorded laser excitation spectra of transitions from the ground X(1)Sigma(+) state of gaseous gold fluoride (AuF) into three excited electronic states in the visible region. We prepared the sample in a dc electric discharge by flowing a dilute mixture of SF(6) in argon through a hollow gold cathode. Two of these electronic states give rise to the previously reported yellow bands of the molecule, for which a rotational analysis is given here for the first time. We have analyzed the (0,0), (1,1), (0,1), and (1,2) bands of these two transitions, which we identify as [17.8]0(+)-X(1)Sigma(+) and [17.7]1-X(1)Sigma(+); their red-degraded (0,0) band heads lie at 563.0 and 566.2 nm, respectively. The (0,0) band of a new, red-degraded [14.0]1-X(1)Sigma(+) transition at 715.1 nm has also been recorded and analyzed. An accurate set of molecular constants of the three excited states as well as the ground state has been determined by least-squares fitting all of the optical data together with measurements made by other workers of the pure rotational spectrum of AuF in its ground state. These constants include the electronic term energies, vibrational frequencies, rotational constants, and Omega-doubling constants. We discuss the nature of these three excited electronic states in terms of the ionic Au(+)F(-) electronic configurations from which they are derived.

Electronic spectrum of AuF: hyperfine structure of the [17.7]1 state.

The [17.7]1-X(1)Sigma(+) (0,0) band of AuF at 566 nm has been studied by laser excitation spectroscopy. The molecule was prepared in a dc electric discharge by flowing a dilute mixture of SF(6) in argon through a hollow gold cathode. The rotational structure of the band has been analyzed for the first time, yielding accurate values for the rotational and Omega-type doubling constants of the upper state. Hyperfine splittings arising from both the (197)Au and (19)F nuclei have been resolved by recording the spectrum at sub-Doppler resolution using the technique of intermodulated fluorescence spectroscopy. The hyperfine structure is dominated by the (197)Au magnetic dipole interaction in the [17.7]1 state, with the (197)Au magnetic hyperfine constant determined to be h(1) = -543(4) MHz. It is demonstrated that the negative value of this constant implies that the [17.7]1 state has significant (3)Delta(1) character and that spin-orbit mixing with a (1)Pi(1) state may be providing the transition intensity to the ground electronic state.

Electronic spectrum of TaO and its hyperfine structure.

The B (2)Phi(5/2)-X(1) (2)Delta(3/2)(0,0) band at 778 nm and the C (2)Delta(3/2)-X(1) (2)Delta(3/2)(0,0) band at 737 nm of tantalum oxide (TaO) were recorded by laser excitation spectroscopy using a hollow cathode sputtering source to generate the molecules. The hyperfine structure arising from the (181)Ta (I=72) nucleus was measured at sub-Doppler resolution using the technique of intermodulated fluorescence spectroscopy. The hyperfine structure was assigned and fitted in order to derive accurate values for the magnetic dipole and electric quadrupole interactions. The magnetic hyperfine constant for the ground electronic state was also calculated using the density functional theory as h(3/2)=625 MHz, in good agreement with the experimental value of 647+/-10 MHz. This result suggests that the X (2)Delta ground state of TaO is well described by a pure deltasigma(2) electronic configuration, where the unpaired electron is located in a Ta 5ddelta orbital.

The ultraviolet spectrum of the CoCl2 radical, studied at vibrational and rotational resolution.

The laser excitation spectrum of the 327 nm band system of CoCl2, formed in a free-jet expansion, has been recorded at a rotational temperature of approximately 10 K. The spectrum is congested and suffers extensive perturbations. A progression in the excited state symmetric stretching vibration has been identified. The decrease in the symmetric stretching vibrational wave number on excitation is considerable [nu1 '=195.7(12), nu1 (")=358.1(17) cm(-1)]. Despite widespread perturbations in the rotational structure of these vibronic bands, they can be confidently assigned to a parallel Omega=72-72 transition, consistent with an inverted 4Deltag ground electronic state. The rotational constant for Co35Cl2 in the ground state is determined to be 0.056 65(11) cm(-1), which corresponds to a value for the zero-point averaged Co-Cl bond length r0 of 2.062 8(40) A. The perturbations are found to be strongly isotopomer dependent.