Rotational fine, and hyperfine analyses of the (0,0) band of the D 3Π-X 3Δ system of vanadium mononitride

Article abstract of DOI:10.1063/1.465138

The VN molecule has been produced in a molecular beam apparatus using a laser vaporization source and its D ³Π-X ³Δ(0,0) band has been studied by laser-induced fluorescence at low (ca. 0.1 cm^-1) and sub-Doppler resolution (ca. 0.004 cm^-1).Lifetimes of single rotational levels of the D ³Π₀ component have been measured and interpreted.Rotational, fine, and hyperfine structures is six of the nine subbands possible for a ³Π <- ³Δ transition have been recorded.Both states exhibit a rapid transition from case (a) -> case (b) coupling cases, manifestedby reversals in the Lande patterns of the hyperfine structure.The data have been reduced to a set of 35 molecular constants using a modified case (a_β) effective Hamiltonian in which two additional magnetic hyperfine parameters are required for each state.The distortions in the hyperfine structure are due almost entirely to second-order spin-orbit interaction between states arising from the same configuration.Analysis of the derived parameters indicates that the X ³Δ state is well represented by the single electron configuration ...8?² 3?⁴ 9?¹ 1δ¹, in which the 9? molecular orbital (MO) is a V 4s-4p hybrid (88percent V 4s) and the 1δ MO is a pure V 3d orbital; the dominant configuration for the D ³Π state is ...8?² 3?⁴ 1δ¹ 4?¹, in which the 4? MO is an antibonding orbital composed of at most 82percent V 3d?.The isoconfigurational a ¹Δ and e ¹Π states are calculated to lie 3390 and 2200 cm^-1 above their respective high spin companions.The lambda doubling in the D ³Π₀ component has been interpreted in terms of spin-orbit interactions with the B ³Σ^- and d ¹Σ⁺ states, both states arisingfrom the ... 8?² 3?⁴ 1δ² configuration; the d ¹Σ⁺ state is known to lie 102 cm^-1 above D ³Π₀, while the B ³Σ^- state probably lies about 8000 cm^-1 below.

Full text of DOI:10.1063/1.465138

Rotational, fine, and hyperfine analyses of the (0,0) band of the D 3Π–X 3Δ system
of vanadium mononitride
Walter J. Balfour, Anthony J. Merer, Hideaki Niki, Benoit Simard, and Peter A. Hackett
Citation: The Journal of Chemical Physics 99, 3288 (1993); doi: 10.1063/1.465138
View online: http://dx.doi.org/10.1063/1.465138
View Table of Contents: http://scitation.aip.org/content/aip/journal/jcp/99/5?ver=pdfcov
Published by the AIP Publishing
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