激光电离碘甲烷中空间电荷对飞行时间质谱峰的影响研究

Space-Charge Effect on Mass Peak Broadening and Shift in Laser Ionization of Methyl Iodide

  • 摘要: 利用飞行时间质谱(TOFMS)研究碘甲烷分子激光电离的过程中,发现I+离子峰的峰形随激光光强增大逐渐加宽,且CHq+ (q=0~3)离子峰位置随光强增大而发生移动。激光功率密度从1.4×1010 W/cm2增加到5.2×1010 W/cm2时,I+离子峰的半高全宽W1/2从113 ns增加到426 ns,同时CH3+离子的峰位置向前位移了52 ns。通过对I+离子峰的半高全宽W1/2和CH3+离子峰位置与碘离子强度II+关系的分析,发现I+离子峰的半高全宽W1/2正比于II+0.5,而CHq+ (q=0~3)的峰位移与碘离子的强度II+成正比。激光焦点处离子间的库仑排斥作用随着离子强度的增大而增大,由于这种空间电荷效应造成的库仑势能的增加对离子的初始平动能有一定影响,并导致离子到达检测器的时间发生改变,因而半高全宽的增大和离子峰位移随离子强度的变化规律,可以用空间电荷效应来解释。

     

    Abstract: The multiphoton ionization of CH3I molecule with 532 nm nanosecond laser was studied by a homemade laser ionization time of flight mass spectrometer. The influence of laser intensity on the full width at half maximum W1/2 of I+ ion peak and the peak position of CHq+ (q=0-3) ions were investigated in details. When laser intensity was increased from 1.4×1010W/cm2 to 5.2×1010W/cm2, the W1/2 of I+ ion was broaden from 113 ns to 426 ns, while the peak position of CH3+ was shifted forward about 52 ns. Through formula derivation and the linear fitting between the peak broadening, peak shift and intensity of I+ ion, the W1/2 of I+ ion is proportional to II+0.5, while the peak shifts of CHq+ (q=0-3) were proportional to II+. At the laser focus, the Coulomb repulsion among the ions increases with the increasing of ion intensity, and the Coulomb potential due to the space charge effect has an influence on the ion kinetic energy, which results in the change of the time of ion reaching the detector. The peak broadening and shift of ions can be well explained by space-charge effect.

     

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