The ν2 bending vibrational structure of the X˜2Σ+ state of MgNC

URI http://harp.lib.hiroshima-u.ac.jp/hiroshima-cu/metadata/12325
ファイル
タイトル
The ν2 bending vibrational structure of the X˜2Σ+ state of MgNC
著者
氏名 FUKUSHIMA Masaru
ヨミ フクシマ マサル
別名 福島 勝
氏名 ISHIWATA Takashi
ヨミ イシワタ タカシ
別名 石渡 孝
キーワード
Fluorescence spectra
Isomerization
Laser induced fluorescence
Wave functions
Parity
抄録

We have generated MgNC in supersonic free jet expansions and observed the laser induced fluorescence(LIF) of the A˜2 – X˜2Σ+ transition. We measured the LIF dispersed spectra from the single vibronic levels of the A˜ 2Π electronic state of MgNC, following excitation of each ν2 bending vibronic band observed, i.e., the κ series of the (0,v′2,0)–(0,0,0), v′2 = 0, 1, 2, 4, and 6 vibronic bands. In the vibrational structure in the dispersed fluorescence spectra measured, the long progression of the ν2 bending mode in the X˜2Σ+ state is identified, e.g., up to v''2=14 in the (0,6,0)–(0,v''2,0) spectrum. This enables us to derive the potential curve of the ν2 bending mode in the X˜2Σ+ state. We used two kinds of models to obtain the potential curve; (I) the customary formula expressed in the polynomial series of the (v''2+(d2/2)) term and (II) the internal rotation model. The potential curve derived from model (I) indicates the convergence of the bending vibrational levels at about 800 cm−1 from the vibrationless level of MgNC, which may correspond to the barrier height of the isomerization reaction, MgNC ⇌ MgCN, in the X˜2Σ+ state. Model (II) gives a simple picture for the isomerization reaction pathway with a barrier height of about 630 cm−1 from the vibrationless level of the more stable species, MgNC. This shows that the v''2=8 bending vibrational level of MgNC is already contaminated by the v''2=2 bending vibrational level of the isomer, MgCN, and implies that the isomerization reaction begins at the v''2=8 level. The bending potential surface and the isomerization reaction pathway, MgNC ⇌ MgCN, in the X˜2Σ+ state are discussed by comparing the potential derived in this study with the surface obtained by quantum chemical calculation.

査読の有無
掲載雑誌名
The Journal of Chemical Physics
135
12
開始ページ
124311-1
終了ページ
124311-11
出版年月日
2011-9-28
出版者
American Institute of Physics
ISSN
0021-9606
NCID
AA00694991
DOI
10.1063/1.3640024
本文言語
英語
資料タイプ
学術雑誌論文
著者版フラグ
出版社版
権利情報
Copyright 2011 American Institute of Physics. This article may be downloaded for personal use only. Any other use requires prior permission of the author and the American Institute of Physics.The following article appeared in J. Chem. Phys. 135, 124311 (2011) and may be found at http://dx.doi.org/10.1063/1.3640024.
関連URL
備考

This research was partially supported by the Ministry of Education, Science, Sports and Culture, Grant-in-Aid for Scientific Research (C), 16510078, 2004 and by Hiroshima City University Grant for Special Academic Research (General Studies), 1102.

区分
hiroshima-cu