Vibrational analysis of SICN X̃ 2Π system

Fukushima, Masaru

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https://hdl.handle.net/2142/91072 Copy

Description

Title

Vibrational analysis of SICN X̃ 2Π system

Author(s)

Fukushima, Masaru

Contributor(s)

Ishiwata, Takashi

Issue Date

2016-06-21

Keyword(s)

Vibrational structure/frequencies

Abstract

• The laser induced fluorescence (~LIF~) spectrum of the $\tilde{A}$ $^2\Delta$ -- $\tilde{X}$ $^2\Pi$ transition was obtained for SiCN generated by laser ablation under supersonic free jet expansion. The vibrational structure of the dispersed fluorescence (~DF~) spectra from single vibronic levels (~SVL's~) was analyzed by numerical diagonalization procedure, in which Renner-Teller (~R-T~), anhamonicity, spin-orbit (~SO~), Herzberg-Teller (~H-T~), Fermi, and Sears interactions have been considered, where the Sears resonance is a second-order interaction combined from SO and H-T interactions with $\Delta K = \pm1$, $\Delta \Sigma = \mp1$, and $\Delta P = 0$. Four vibronic levels, $(01^10) \
• \mu \
• \Sigma_{\frac{1}{2}}^{(-)}$, $\kappa \
• \Sigma_{\frac{1}{2}}^{(+)}$, $(02^00) \
• \mu$ and $\kappa \
• \Pi_{\frac{1}{2}}$, are almost closed within the four basis functions by R-T and Sears interactions (~i.e.~the four-by-four transformation matrix below is close to ortho-normal~)
• \kappa \
• 2, +2 \rangle \end{array} \right) \notag \
• v_2, l \rangle$ are basis functions of electronic, electron spin, and two dimensional harmonic oscillator, respectively. \if0 The two levels, $(01^10) \
• \Sigma_{\frac{1}{2}}^{(+)}$ and $(02^00) \
• \Pi_{\frac{1}{2}}$, with $\Delta K = \pm1$ and $\Delta P = 0$, show typical example of Sears resonance with an almost one-to-one mixing
• 2, 0 \rangle \end{array} \right) \
• + \
• , \end{equation} where the off-diagonal terms are caused by Sears resonance, while the diagonals are came from R-T mostly. \fi The mixing coefficients of the two vibronic levels agree with those obtained from computational studies\footnote{V.~Brites, A.~O.~Mitrushchenkov, and C.~L\'{e}onard, J.~Chem.~Phys. 138, 104311 (2013)
• C.~L\'{e}onard, Private communication.}. The two levels among the four above, $(01^10) \
• \Pi_{\frac{1}{2}}$, with $\Delta K = \pm1$ and $\Delta P = 0$, show typical example of Sears resonance with an almost one-to-one mixing. Even for levels lying at $\sim$ 1,000 cm$^{-1}$, some of them are mixed heavily and widely with several levels, and their vibrational quantum numbers are thus meaningless.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

En

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http://hdl.handle.net/2142/91072

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Copyright 2016 by the authors

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