Mass resolution of linear quadrupole ion traps with round rods

RATIONALE: Auxiliary dipole excitation is widely used to eject ions from linear radio-frequency quadrupole ion traps for mass analysis. Linear quadrupoles are often constructed with round rod electrodes. The higher multipoles introduced to the electric potential by round rods might be expected to change the ion ejection process. We have therefore investigated the optimum ratio of rod radius, r, to field radius, r(0), for excitation and ejection of ions. METHODSTrajectory calculations are used to determine the excitation contour, S(q), the fraction of ions ejected when trapped at q values close to the ejection (or excitation) q. Initial conditions are randomly selected from Gaussian distributions of the x and y coordinates and a thermal distribution of velocities. The N=6 (12 pole) and N=10 (20 pole) multipoles are added to the quadrupole potential. Peak shapes and resolution were calculated for ratios r/r(0) from 1.09 to 1.20 with an excitation time of 1000cycles of the trapping radio-frequency. RESULTSRatios r/r(0) in the range 1.140 to 1.160 give the highest resolution and peaks with little tailing. Ratios outside this range give lower resolution and peaks with tails on either the low-mass side or the high-mass side of the peaks. This contrasts with the optimum ratio of 1.126-1.130 for a quadrupole mass filter operated conventionally at the tip of the first stability region. With the optimum geometry the resolution is 2.7 times greater than with an ideal quadrupole field. Adding only a 2.0% hexapole field to a quadrupole field increases the resolution by a factor of 1.6 compared with an ideal quadrupole field. Addition of a 2.0% octopole lowers resolution and degrades peak shape. With the optimum value of r/r(0), the resolution increases with the ejection time (measured in cycles of the trapping rf, n) approximately as R-0.5=6.64n, in contrast to a pure quadrupole field where R-0.5=1.94n. CONCLUSIONSAdding weak nonlinear fields to a quadrupole field can improve the resolution with mass-selective ejection of ions by up to a factor of 2.7. The optimum ratio r/r(0) is 1.14 to 1.16, which differs from the optimum ratio for a mass filter of 1.128-1.130. Copyright (c) 2014 John Wiley & Sons, Ltd.