### Abstract

The (1, 0) band of the B^{4}Π-X^{4}Σ^{-} transition of VO has been analyzed rotationally, from Doppler-limited discharge emission and laser excitation spectra. The B^{4}Π, v = 1 level is heavily perturbed by a vibrational level of the a^{2}Σ^{+} state and, with the extra complexity caused by the ^{51}V nuclear hyperfine structure, could be analyzed fully only by extensive wavelength-resolved laser-induced fluorescence experiments. Making use of data from the corresponding perturbations in B^{4}Π, v = 0 and assuming that the vibrational dependence of the spin-orbit matrix element can be represented by a vibrational overlap integral, it has been possible to deduce the vibrational numbering of the perturbing a^{2}Σ^{+} state without having to use isotopic data. It is found that the a^{2}Σ^{+}, v = 0 level lies near 10412 cm^{-1}, and that B^{4}Π, v = 1 is perturbed by a^{2}Σ^{+}, v = 3. The a^{2}Σ^{+} state comes from the same electron configuration, (4sσ) (3dδ)^{2}, as the X^{4}Σ^{-} ground state. The phases of the spin-orbit matrix elements between ^{4}Π and ^{2}Σ^{+} states must be chosen consistently in order to obtain a correct understanding of the rotational perturbations. A consistent set of phases is obtained with 〈^{2}Σ^{+}, F_{2} | H_{SO} | ^{4}Π_{1/2}, f〉 = 〈^{2}Σ^{+}, F_{1} | H_{SO} | ^{4}Π_{12}, e〈 = [formula]〉^{2}Σ^{+}, F_{2} | H_{SO} | ^{4}Π_{- 1 2}, f〈 = -〉^{2}Σ^{+}, F_{1} | H_{SO} | ^{4}Π_{- 1 2}, e〈 = A/2, where A = 〉^{2}Σ^{+} П H_{spin-orbit} П ^{4}Π〈.

Original language | English |
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Pages (from-to) | 443-458 |

Number of pages | 16 |

Journal | Journal of Molecular Spectroscopy |

Volume | 163 |

Issue number | 2 |

DOIs | |

Publication status | Published - 1994 |

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## Cite this

^{4}Π-x

^{4}Σ

^{-}(1, 0) band of vo.

*Journal of Molecular Spectroscopy*,

*163*(2), 443-458. https://doi.org/10.1006/jmsp.1994.1039