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首页> 外文期刊>The Journal of Chemical Physics >Rovibronically selected and resolved two-color laser photoionization and photoelectron study of titanium monoxide cation
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Rovibronically selected and resolved two-color laser photoionization and photoelectron study of titanium monoxide cation

机译：用机械振动选择和解析一氧化钛阳离子的双色激光光电离和光电子研究

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Two-color visible-ultraviolet (VIS-UV) resonance-enhanced laser photoionization and pulsed field ionization-photoelectron (PFI-PE) study of gaseous titanium monoxide (TiO) in the total energy range of 55 000-57 320 cm~(-1) has been conducted. The TiO molecules were selectively excited to single J′ rotational levels of the intermediate TiO(B ~3Π_1, ν′ 0) state by using a VIS dye laser and then ionized by using another UV laser. This two-color photoexcitation method has allowed the measurement of cleanly J-resolved PFI-PE spectra for the TiO(X ~2Δ_(52,32); v 0, 1, and 2) vibrational bands. By simulating the rotationally resolved PFI-PE spectra, J 32 is determined to be the lowest rotational level of the ground electronic state, confirming that the symmetry of the TiO ground state is ~2Δ_(32). Irregular intensity patterns for rotational PFI-PE peaks that deviated from the regular patterns that favor the rotational transitions with small change of the core rotational angular momentum, are observed. This observation is indicative of strong perturbations of the PFI-PE rotational transitions, possibly by a channel-coupling mechanism. The analysis of the PFI-PE spectra yields highly precise values for the adiabatic ionization energy of TiO IE(TiO) 55 005.4 ± 0.8 cm~(-1) (6.81980 ± 0.00010 eV), and the vibrational frequency (ω_e 1056.1 ± 0.8 cm~(-1)), the anharmonicity constant (ω_eχ_e 4.4 ± 0.8 cm~(-1)), the rotational constants (B_e 0.5613 ± 0.0009 cm~(-1) and α_e 0.0029 ± 0.0008 cm ~(-1)), and the equilibrium bond length (r_e 1.583 ?) for the TiO(X ~2Δ_(32)) ground state, the vibrational frequency (ω_e 1058.4 ± 0.8 cm~(-1)), the anharmonicity constant (ω_eχ_e 5.1 ± 0.8 cm~(-1)), the rotational constants (B_e 0.5715 ± 0.0007 cm~(-1) and α_e 0.0030 ± 0.0004 cm~(-1)) and the equilibrium bond length (r_e 1.568 ?) for the excited spin orbit state TiO(X ~2Δ52), along with the spin-orbit coupling constant (A 105.9 ± 0.2 cm~(-1)) for TiO(X ~2Δ52,32).
机译：气态一氧化钛（TiO）在总能量范围为55 000-57 320 cm〜（- 1）已进行。通过使用VIS染料激光将TiO分子选择性激发至中间TiO（B〜3Π_1，ν'0）状态的单个J'旋转能级，然后使用另一个UV激光将其电离。这种双色光激发方法允许测量TiO（X〜2Δ_（52,32）; v 0、1和2）振动带的干净J分辨PFI-PE光谱。通过模拟旋转解析的PFI-PE光谱，可以确定J 32为基态电子态的最低旋转电平，从而确认TiO基态的对称性约为〜2Δ_（32）。观察到旋转的PFI-PE峰的强度分布不规则，这些峰偏离规则的模式，这些规则的模式有利于在核心旋转角动量变化很小的情况下实现旋转过渡。该观察结果表明可能是通过通道耦合机制对PFI-PE旋转过渡产生强烈干扰。通过对PFI-PE光谱的分析，可以获得TiO绝热电离能的高精度值IE（TiO）55 005.4±0.8 cm〜（-1）（6.81980±0.00010 eV）和振动频率（ω_e1056.1±0.8 cm） 〜（-1）），非谐常数（ω_eχ_e4.4±0.8 cm〜（-1）），旋转常数（B_e 0.5613±0.0009 cm〜（-1）和α_e0.0029±0.0008 cm〜（-1））， TiO（X〜2Δ_（32））基态的平衡键长度（r_e 1.583？），振动频率（ω_e1058.4±0.8 cm〜（-1）），非谐常数（ω_eχ_e5.1±0.8 cm〜 （-1）），激发自旋轨道态TiO（b_e 0.5715±0.0007 cm〜（-1）和α_e0.0030±0.0004 cm〜（-1））和平衡键长（r_e 1.568？）。 X〜2Δ52），以及TiO（X〜2Δ52,32）的自旋轨道耦合常数（A 105.9±0.2 cm〜（-1））。

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