三维离子阱内空间电荷效应的理论分析

Theoretical Analysis of the Space Charge Effect in 3D Ion Trap

  • 摘要: 离子阱内存储的大量离子之间会有强烈的库仑相互作用,导致所谓的空间电荷效应,它一直是质谱理论研究和应用领域内非常感兴趣的问题。本工作根据三维离子阱内的离子分布情况,假设离子在三维离子阱的中心区域呈近似于球对称的高斯分布, 通过求解阱内电场所对应的电势函数满足的泊松方程,得到这个球对称高斯分布的离子云所产生的电场解析表达式,在小振动近似下,得到离子运动的久期(secular)频率与阱内离子数目的理论关系。通过进一步应用Mathematica数学模拟软件,计算模拟了不同久期运动频率的离子在不同个数的离子所组成的离子云排斥作用下的久期主频率的移动。计算结果与小振动近似下的理论计算结果基本一致。由于离子阱的质量分析是通过改变离子偶极激发电压实现的,这种频率移动将对离子被激发逸出的电压值产生影响,最终影响离子阱质谱质量分析的准确度。因此,用离子阱质谱进行离子分析时,通过减少存储的离子数以减少空间电荷效应,或根据离子数对质谱测量结果进行校正是有意义的。

     

    Abstract: The strong Coulombrepulsion among a large number of ions stored in an ion trap leads to the so-calledspace-charge effect. This effect is of theoretical and practical importance inmass spectrometry since it significantly distorts the mass accuracy andsensitivity of an ion trap mass analyzer. However, it is very difficulty to getan analytical solutions for the ion motion in the presence of the space chargeeffect because of their many-body problem. In this article, a model for thespace charge effect is given and discussed. A spherically symmetric Gaussiandistribution of the ions in the center of a three-dimensional ion trap wasassumed, and the potential field due to the ion cloud was calculatedanalytically by solving the Poisson equation. Based on the small vibrationapproximation and the potential field calculation, a relationship between thefrequency shift of ion secular motion and the number of ions in the trap wasderived analytically.For comparison, the frequency shift was also calculatednumerically using Mathematica. The result was similar to that obtained with thesmall-vibration approximation. For an ion trap mass analysis using dipoleexcitation, the frequency of ion secular motion strongly affects the excitationvoltage, and in turn the accuracy and sensitivity of mass analyzer. Theperformance of an ion trap mass analyzer could be improved by reducing thenumber of stored ions, or using the corrections based on theoreticalcalculation.

     

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