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Ion Cyclotron Resonance Power Absorption: Collision Frequencies for CO2+, N2+, and H3+Ions in Their Parent Gases

机译:离子回旋共振功率吸收:母体气体中CO2+、N2+和H3+离子的碰撞频率

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The complete solution for the equation of motion of an ion in the ICR cell is shown to give results for the instantaneous power absorption in excellent agreement with experiment at all pressures. The instantaneous power absorption at resonance initially increases linearly with time, and at high pressures levels off to a constant value at saturation where the energy gained by ions from the rf electric field is equal to the energy dissipated in collisions. An expression is also derived for the average kinetic energy of an ion at saturation in the steady‐state limit. Pulsed ICR techniques are used to obtain the instantaneous power absorption curves forN2+, CO2+, andH3+ions in their parent gases as a function of pressure, from which are calculated the momentum transfer rate constantsk, and the dependence of the rate constants on ion kinetic energy. At 293°K,k(N2+)=k(CO2+)=0.67×10−9 cm3 molecule−1·sec−1, andk(H3+)=1.09×10−9 cm3 molecule−1·sec−1. ForN2+ions in N2andCO2+ions in CO2, the rate constants are both significantly greater than that predicted by polarization theory and both rate constants increase significantly with increasing ion kinetic energy. This behavior is most likely a consequence of long‐range resonant charge transfer outside the orbiting impact parameter.
机译:ICR池中离子运动方程的完整解给出了在所有压力下与实验非常吻合的瞬时功率吸收结果。共振时的瞬时功率吸收最初随时间线性增加,在高压下趋于稳定,达到饱和时的恒定值,其中离子从射频电场获得的能量等于碰撞中耗散的能量。还推导了稳态极限下离子饱和时的平均动能的表达式。脉冲ICR技术用于获得母气中N2+、CO2+和H3+离子随压力变化的瞬时功率吸收曲线,由此计算动量传递速率常数sk,以及速率常数对离子动能的依赖性。在 293°K 时,k(N2+)=k(CO2+)=0.67×10−9 cm3 分子−1·sec−1,和k(H3+)=1.09×10−9 cm3 分子−1·sec−1。对于N2中的N2+离子和CO2中的CO2+离子,速率常数均显著大于极化理论预测的速率常数,并且速率常数均随离子动能的增加而显著增加。这种行为很可能是长距离谐振电荷转移超出轨道冲击参数的结果。

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