FOURIER TRANSFORM UV EMISSION SPECTROSCOPY OF THE $B{^{2}}\Sigma^{+} - X^{2}\Sigma^{+}$ BAND OF THE $PN^{+}$

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1998

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Ohio State University

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High resolution Fourier transform emission spectrum of the B2Σ+X2Σ+ band of the PN+ ion was observed in the ultra violet region around 31000cm−1 with Bruker IFS120HR. The rotationally resolved spectrum of PN+, produced by an ac discharge of the PCl3,N2, and He gas mixture, was recorded for about 11 h accumulating the interferogram 1600 times. The monochromator placed just before a photomultiplier worked effectively as an optical filter with a band width of 200cm−1. The (0,0) band lines split into doublet due to the spin-rotation splitting were assigned to the R- and P- branch lines of N'' up to 35. The determined band origin ν0=31058.9963(81)cm−1 is consistent with the previous low resolution result [1]. The rotational, centrifugal distortion constants for both states were determined as well as the spin-rotation constant for the ground state. The B2Σ+ state has weaker bond than that of the ground state, since the bond length of the B2Σ+(v=0) state (1.570 {\AA}) is by 0.076 {\AA} longer, and the force constant (k=2.90 mdyne/{\AA}) is by about 70% smaller than those of the ground state. Present results support the ab initio calculation which predicts a shallow minimum for the B2Σ state due to avoided crossing [2]. 1. I.K. Ahmad and P.A. Hamilton, J. Mol. Spectrosc., 163, 214 (1994). 2. F. Grein, Chem. Phys. Lett., 120, 383 (1998).

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Author Institution: Department of Chemistry, Faculty of Science, Kyushu University

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