The nonlinear harmonics within the ion motion are the fingerprint of the nonlinear fields. They are exclusively introduced by these nonlinear fields and are responsible to some specific nonlinear effects such as nonlinear resonance effect. In this article, the ion motion in the quadrupole field with a weak superimposed octopole component, described by the nonlinear Mathieu equation (NME), was studied by using the analytical harmonic balance (HB) method. Good accuracy of the HB method, which was comparable with that of the numerical fourth-order Runge-Kutta (4th RK), was achieved in the entire first stability region, except for the points at the stability boundary (i.e., β = 1) and at the nonlinear resonance condition (i.e., β = 0.5). Using the HB method, the nonlinear 3β harmonic series introduced by the octopole component and the resultant nonlinear resonance effect were characterized. At nonlinear resonance, obvious resonant peaks were observed in the nonlinear 3β series of ion motion, but were not found in the natural harmonics. In addition, both resonant excitation and absorption peaks could be observed, simultaneously. These are two unique features of the nonlinear resonance, distinguishing it from the normal resonance. Finally, an approximation equation was given to describe the corresponding working parameter, qnr, at nonlinear resonance. This equation can help avoid the sensitivity degradation due to the operation of ion traps at the nonlinear resonance condition.
We recently described a new electrically compensated trap in FT ion cyclotron resonance mass spectrometry and developed a means of tuning traps of this general design. Here, we describe a continuation of that research by comparing the ion transient lifetimes and the resulting mass resolving powers and signal-to-noise (S/N) ratios that are achievable in the compensated vs. uncompensated modes of this trap. Transient lifetimes are ten times longer under the same conditions of pressure, providing improved mass resolving power and S/N ratios. The mass resolving power as a function of m/z is linear (log-log plot) and nearly equal to the theoretical maximum. Importantly, the ion cyclotron frequency as a function of ion number decreases linearly in accord with theory, unlike its behavior in the uncompensated mode. This linearity should lead to better control in mass calibration and increased mass accuracy than achievable in the uncompensated mode. 相似文献
Ion isolation in a linear ion trap is demonstrated using dual resonance frequencies, which are applied simultaneously. One frequency is used to eject ions of a broad m/z range higher in m/z than the target ion, and the second frequency is set to eject a range of ions lower in m/z. The combination of the two thus results in ion isolation. Despite the simplicity of the method, even ions of low intensity may be isolated since signal attenuation is less than an order of magnitude in most cases. The performance of dual frequency isolation is demonstrated by isolating individual isotopes of brominated compounds.
In a pH=0.65―1.5 NaAc-HCl medium, methylene blue(MB) reacts with 12-tungstophosphoric acid (TPA) by virtue of electrostatic attraction and hydrophobic force to form a 3:2 ion-association complex. As a result, the intensities of resonance Rayleigh scattering(RRS), second-order scattering(SOS) and frequency doubling scatte- ring(FDS) are enhanced greatly. The maximum scattering wavelengths of RRS, SOS and FDS are located at 316, 647 and 311 nm. The increments of scattering intensity(△I) are directly proportio... 相似文献
Boundary-Activated Dissociation (BAD) of multiple charge ions has been investigated in a low pressure linear ion trap (LIT) in the presence of nonlinear DC fields. Nonlinear DC fields allowed ions to be stored for a long duration at working points beyond the βy?=?0 stability boundary of the regular quadrupole fields. The ions reached large stable radial amplitude trajectories gaining high kinetic energies from the drive RF field. This led to collision activation and the formation of fragments. Experimental and simulation data showed that the degree of fragmentation was strongly dependent on the q value, Mathieu stability parameter, and the strengths of nonlinear fields. In the absence of the nonlinear fields the fragmentation efficiency was 0?% at q?=?0.23 and 17?% at q?=?0.4. In the presence of nonlinear fields BAD efficiency increased to up to 94?% at q?=?0.23 and 84?% at q?=?0.4. The broadening of the stability diagram at the βy?=?0 boundary also enabled the observation of fragment ions with higher mass-to-charge ratios (m/z) than the m/z of the precursor ions thus overcoming a major drawback of BAD of multiple-charged ions. 相似文献
Collision-induced dissociation (CID) of ions by resonance activation in a quadrupole ion trap is usually accomplished by resonance exciting the ions to higher kinetic energy, whereby the high kinetic energy ions collide with a bath gas, such as helium or argon, inside the trap and dissociate to fragments. A new ion activation method using a well-defined rectangular wave dipolar potential formed by dividing down the trapping rectangular waveform is developed and examined herein. The mass-selected parent ions are resonance excited to high kinetic energies by simply changing the frequency of the rectangular wave dipolar potential and dissociation proceeds. A relationship between the ion mass and the activation waveform frequency is also identified and described. This highly efficient (CID) procedure can be realized by simply changing the waveform frequency of the dipolar potential, which could certainly simplify tandem mass spectrometry analysis methods.
The nonlinear dielectric effect (NDE) has been applied to study the molecular association in tetrahydrofuran (THF) solutions in benzene and in cyclohexane. On the basis of the experimental values of the NDE parameter, electric permittivity, and density, determined as a function of temperature and concentration, and applying the general, statistical theory of NDE, the association constants and dipole moments of the associates were determined. The molecular orbital PM3 method has been applied to calculate the dipole moments and energy of molecular clusters. The results of NDE and PM3 studies are fairly consistent and reveal that a weak dipolar association takes place in the cyclohexane solutions. In the benzene solutions the association, if any, is much weaker probably due to competitive interactions between the solute and the solvent. 相似文献
Paul trap working in the second stability region has long been recognized as a possible approach for achieving high-resolution mass spectrometry (MS), which however is still far away from the experimental implementations because of the narrow working area and inefficient ion trapping. Full understanding of the ion motional behavior is helpful for solving the problem. In this article, the ion motion in a superimposed octopole field, which was characterized by the nonlinear Mathieu equation, was solved analytically using Poincare-Lighthill-Kuo (PLK) method. This method equivalently described the nonlinear disturbance by an effective quadrupole field with perturbed Mathieu parameters, au′ and qu′, which would bring huge convenience in the studies of nonlinear ion dynamics and was, therefore, used for rapid evaluation of the nonlinear effects of ion motion. Fourth-order Runge-Kutta method (4th R-K) indicated the error of PLK for characterizing the frequency shift of ion motion was within 15%. Figure
Examination of the collisional cooling effect of the buffer gases on ion trapping and detection in an ion trap mass spectrometer has been undertaken by the SIMION 3D program. Computation for the kinetic energy of ions under various conditions was used to account for the effects of collisional cooling of ions. Several parameters that may affect the collisional cooling effects of ions are evaluated including the existence and the variation of pressure of the buffer gas; the temperature of the ion trap; the size of the inner radius of the ion trap electrodes; the mass to charge ratio of ions; the alternative buffer gases and the qz. values which establish the ion trap trapping environment. 相似文献
The Planar electrostatic ion trap expands the trapping space of the linear electrostatic ion trap, giving rise to higher tolerance to space charge. A rotational symmetrical design was made, which has a trapping field between two layers of concentric circular electrodes, and the ions are trapped to oscillate around the center plane between the electrodes. The oscillatory motions of the ions were simulated and the field distribution was optimized to achieve isochronous motion against energy spread in R, z, and φ directions. The image charge signal can be picked up by more than one circular electrode and using FFT the mass resolution for the optimized trap can reach 80,000 FWHM. While Fourier transform of the image charge signal generates many high harmonic peaks, the unwanted harmonic peaks can be eliminated by linear combination of image charge signals from multiple pick-up electrodes to give satisfactory results. 相似文献
