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First detection and analysis of an electronic spectrum of vanadium hydride: The D<sup>5</sup>Π-X<sup>5</sup>Δ (0,0) band.

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A new electronic transition in vanadium fluoride, VF.

Grant A Luce1, James Bradley1, Thomas D Varberg1

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Researchers analyzed gas-phase vanadium fluoride using laser excitation spectroscopy. This study provides the second rotational analysis of a vanadium fluoride electronic transition, determining its molecular constants and bond length.

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Area of Science:

  • Chemical Physics
  • Molecular Spectroscopy
  • Quantum Chemistry

Background:

  • Vanadium fluoride (VF) is a molecule with limited spectroscopic data.
  • Electronic transitions in small transition metal compounds are crucial for understanding bonding and reactivity.

Purpose of the Study:

  • To perform a rotational analysis of the [12.7]5Δ-X5Δ electronic transition of gas-phase vanadium fluoride.
  • To determine precise molecular constants and the bond length of the ground state of VF.

Main Methods:

  • Laser excitation spectroscopy was used to record the [12.7]5Δ-X5Δ (0-0) band of VF at 789 nm.
  • Laser-induced fluorescence was detected via the [12.7]5Δ-X5Δ (0-1) band.
  • An effective Hamiltonian in a Hund's case (a) basis was employed for least-squares fitting.

Main Results:

  • The red-degraded [12.7]5Δ-X5Δ (0-0) band was successfully recorded and analyzed.
  • All five main subbands (∆Ω = 0) were identified, showing only P and R branches characteristic of a parallel transition.
  • The upper state exhibited significant local perturbations.
  • Molecular constants for the X5Δ (v=0,1) and [12.7]5Δ (v=0) levels were determined.
  • The equilibrium rotational constant Be = 0.38324(89) cm⁻¹ and bond length Re = 1.7829(21) Å for the ground state were derived.

Conclusions:

  • This work represents the second reported rotational analysis of an electronic transition in VF.
  • The determined molecular constants and bond length provide valuable data for theoretical and experimental studies of vanadium fluoride.
  • The observed perturbations offer insights into the complex electronic structure of VF.