No description available.

No description available.

The cylindrical ion trap (CIT) is made up of two planar endcap electrodes and a cylindrical ring electrode. The investigation of simpler geometries like CIT has been started off in recent years with a view towards miniaturization. As a step towards this, numerical studies on CITs were carried out in our laboratory. Here in this study, our motive is to characterize a CIT through experiments. We have designed a mass spectrometer where a CIT is used as the mass analyzer. The trap performance was observed by varying six parameters associated with our experiment. The parameters are (1) the ionization voltage, (2) the ramp time, (3) the ionization time, (4) the cooling time, (5) the dead time and (6) the bias voltage applied across the filaments. All the experiments have been performed in the mass selective boundary ejection mode.

This thesis presents results of investigations that have been carried out to understand dynamics in nonlinear Paul trap mass spectrometers. Of the three problems that have been taken up for study in this thesis, the first concerns understanding early/delayed ejection of ions in mass selective boundary ejection experiments. The second looks at the differential resolution observed in forward and reverse scan resonance ejection experiments. The third study explores a coupled nonlinear resonance within the nominally stable region of trap operation. The method of multiple scales has been to elucidate dynamics associated with early and delayed ejection of ions in mass selective ejection experiments in Paul traps. We develop a slow flow equation to approximate the solution of a weakly nonlinear Mathieu equation to describe ion dynamics in the neighborhood of the stability boundary of ideal traps (where the Mathieu parameter qz = qz* = 0.908046). For positive even multipoles in the ion trapping field, in the stable region of trap operation, the phase portrait obtained from the slow flow consists of three fixed points, two of which are saddles and the third is a center. As the qz value of an ion approaches qz*, the saddles approach each other, and a point is reached where all nonzero solutions are unbounded, leading to an observation of early ejection. The phase portraits for negative even multipoles and odd multipoles of either sign are qualitatively similar to each other and display bounded solutions even for qz > qz*, resulting in the observation of delayed ejection associated with a more gentle increase in ion motion amplitudes, a mechanism different from the case of the positive even multipoles. The second study investigates constraints on pre-ejection dynamical states which cause differential resolution in resonance ejection experiments using Paul traps with stretched geometry. Both analytical and numerical computations are carried out to elucidate the role of damping and scan rate in influencing coherence in ion motion associated with the forward and reverse scan. It has been shown that in the forward scan experiments, for a given damping, low scan rates result in coherent motion of ions oof a given mass at the jump point. At this point, the amplitude and phase of ions of a given mass, starting at different initial conditions, become effectively identical. As the scan rate is increased, coherence is destroyed. For a given scan rate, increasing damping introduces coherence in ion motion, while decreasing damping destroys this coherence. In reverse scan experiments, for a given damping, very low scan rates will cause coherent ion motion. Increasing the scan rate destroys this coherence. The effect of damping in reverse scan experiments is qualitatively similar to that in the forward scan experiments, but settling times in the forward scan are shorter, leading to improved coherence and resolution. For mass spectrometrically relevant scan rates and damping values, significantly greater coherence is obtained in the forward scan. In the third study we investigate the weakly coupled and nonlinear Mathieu equations governing ion motion in axial and radial directions in a Paul trap in the neighborhood of a nonlinear resonance point at az* = -0.2313850427 and qz* = 0.9193009931$. Using harmonic balance based approximate averaging up to second order; we obtain a slow flow that, we numerically demonstrate, approximates the actual ion dynamics. We find that the slow flow is Hamiltonian. We study the slow flow numerically with the objective of exploring and displaying some of the possible types of interesting ion motions. In particular, we choose specific but arbitrary parameter values; study the stability of the individual radial and axial motion invariant manifolds; examine the rather large times associated with escape of ions; notice regions in the averaged phase space wherein trajectories do not, in fact, escape; observe apparently chaotic dynamics preceding escape for ions that do escape; and note that trajectories that do not escape appear to be confined to 4-tori. We conclude with some comments on the implications for practical operation of the Paul trap near this resonant point.

A Paul trap mass spectrometer has a three-electrode geometry mass analyzer consisting of two identical end cap electrodes and a ring electrode. Traditionally, the two end cap electrodes are electrically grounded and an RF potential is applied to the central ring electrode to generate the "trapping field". Ions of the analyte sample are formed in situ by electron bombardment and mass analysis of the fragment ions is performed by mass selectively destabilizing the ions from the trap. The inhornogeneities present in the trapping field (introduced either by misalignment of the trap geometry or by applying a dipolar auxiliary excitation across the end cap electrodes) give rise to various interesting phenomena including, resonance ejection of the trapped ions This thesis is concerned with taking a look into the experimental aspects associated with resonance ejection of ions caused by the dipolar excitation Additionally, u also reports the work undertaken to develop necessary instrumentation for resonant excitation experiments and my contribution to operational>zc the Paul trap mass spectrometer fabricated in the laboratory. The thesis is divided into 5 chapters. Chapter 1 is an introductory chapter. After discussing the conditions for stability of the trapped ions, it goes on to present a brief survey of a variety of applications in literature, which have used resonant excitation. Towards the end, the motivation of the present effort and the scope of work in the thesis have been spelt out. This includes (a) redesign of the ion detector electronics, (b) design of an auxiliary excitation generator, and (c) studies on resonance ejection. Chapter 2 outlines the design considerations, circuit description and fabrication details for the ion detector electronics. The circuits presented in this chapter include (a) electrometer amplifier and (b) -3 kV DC supply for the electron multiplier detector. The electrometer amplifier amplifies the ion current signal from the electron multiplier detector and it needs to have a high input impedance and a high slew rate. The electron multiplier detector requires -3 kV DC power supply for operation. The -3 kV DC power supply is required to have a regulated output voltage with low ripple in the output. Chapter 3 presents the design considerations, circuit description and fabrication details for the auxiliary excitation generator. The auxiliary excitation generator is a three channel DDS (Direct Digital Synthesis) oscillator with independent control of frequency amplitude, and phase of the output signal. Chapter 3 also discusses the micro controller based control sub-system that allows the user to set above mentioned output parameters. The control sub-system provides a user-friendly keyboard interface and 2-line alphanumeric LCD display per channel. It also provides various bus interfaces (such as I2C and SPI) to interface with DDS oscillator ICs, amplitude control DAC, and LCD displays. The chapter then goes on to describe the implementation details of the software written for the control sub-system. The hardware design is simplified by using a micro controller as heart of the control sub-system and employing the software to handle the complex functions. As an example, the design of the keyboard interface is simplified by directly connecting a matrix keyboard to the input/output port of the micro controller. The software is used to scan the keyboard, detect key press and find out the key pressed. Nonetheless, in order to meet specific performance required for the present work, the software needs to have a sense of time, be portable and scalable. Details of the "layered" architecture adopted by as to meet these specific requirements, the lower level "driver" functions implemented for various interfaces of the control sub-system, and the higher level or the "application" software, are described. The application software uses the driver functions to accomplish various tasks required to be executed by the control sub-system. Finally, the chapter presents the design consideration and fabrication details of the coupling transformer used to couple the output of the auxiliary excitation generator to the Paul trap Chapter 4 describes the resonant excitation experiments performed as part of the present work. First of all the chapter presents the improvement in the performance of the Paul trap mass spectrometer as a result of redesigned ion detector electronics It is seen that the resolution is improved significantly due to the improved response time of the electrometer amplifier. The chapter then describes the effect of the resonant excitation on the ions and also that the frequency of the applied auxiliary excitation should be between 500 kHz to 125 kHz. Next, a number of mass spectra for different frequencies of the applied auxiliary excitation are presented. These mass spectra indicate that the resonant ejection sets in for lower masses even at lower amplitude of the auxiliary excitation where as higher amplitude is required for the resonant ejection of the higher masses. It is seen that the resonant excitation of ions improves resolution of the mass spectrum. Moreover, the auxiliary excitation results in ejection of the ions at lower amplitude of the RF voltage and thus allows extending the mass range of the mass spectrometer. We present the mass spectrum of CCI4 which is not possible to normally record in our instrument. We also present results intended to understand the relation between frequency and amplitude of the auxiliary excitation on the mass spectra of benzene. Finally, results of an interesting experiment are presented which indicates the presence of the non-linear resonance points in the Paul trap. Chapter 5 presents the concluding remarks. References cited in the thesis are attached in their alphabetical order at the end of the thesis.

No description available.

The thesis aims at building an experimental setup for conducting the boundary ejection and resonance ejection experiments on wide variety of ion trap mass analyzers. The experimental setup has two parts namely power electronics circuits and mechanical assembly. The focus of the thesis is on the electronics hardware which provides various power sources required for the operation of ion trap mass spectrometer. The electronics circuits discussed in the thesis have better performance, flexibility and ruggedness compared to the existing setup. The traditional power supplies used in ion trap mass spectrometers are all linear supplies. But one major drawback of these supplies is the high power dissipation and consequently, the power efficiency degrades. We are trying to introduce switch mode power supplies to reduce the power dissipation loss and eventually increase the power efficiency. In the course of the work the following power supplies have been developed. The supplies are - 1.Constant current source, 2.Filament base, 3.gating power supply and pulsing circuit, 4.High voltage DC power supply and 5. High voltage RF generator.

This thesis presents axially symmetric equivalents of three-dimensional rf ion traps. Miniaturization in mass spectrometry has focused on miniaturizing mass analyzers. Decrease in mass analyzer size facilitates reduction of the size of other components of a mass spectrometer, especially the radio frequency electronics and vacuum system. Miniaturized mass analyzers are made using advanced microfabrication techniques. Due to micromachining limitations, it is not possible to fabricate ion traps with exact axial symmetry. The motivation for this thesis is to investigate newer three-dimensional geometries which do not possess axial symmetry, but are equivalent in performance to axially symmetric ion traps. We introduce a 3D geometry called square ion trap(SIT) having a ring electrode made off our square shaped planar surfaces and square shaped endcap electrodes resembling a cuboid. Initially, a SIT geometry is taken and it will be investigated if this unknown 3D geometry can be made equivalent to a well characterized, axially symmetric ion trap like the CIT. The purpose of showing equivalence will be to understand the ion dynamics and fields inside the new 3D SIT. This thesis consists of five chapters. In Chapter 1, we present the necessary background information required to understand the operation of a mass spectrometer. The Paul trap geometry is introduced followed by the derivation of equation of ion motion inside the Paul trap. The Mathieu stability plot and the modes of operation of a mass spectrometer are briefly discussed. The chapter ends by outlining scope of the thesis. Chapter 2 describes the computational methods employed by us in the thesis. First, the geometry of square ion trap is introduced. Then the boundary element method(BEM) which is used to compute the charge distribution on the electrode surfaces is discussed. This is followed by the three-dimensional Green’s function which should be employed for non-axially symmetric structures. The method to calculate potential and field inside the ion trap from charge distribution is shown. Calculation of multipole coefficients for non-axially symmetric traps using charge distribution is shown. The methods used to generate ion trajectory and stability plot are discussed. The Nelder-Mead simplex method used for optimization is also presented. To verify our numerical methods of charge calculation, we have taken standard textbook problems and compared our results with those presented therein. The multipoles calculation, field and ion trajectory was verified by comparing the results for the Paul trap and cylindrical ion traps. Chapter 3 presents the results for axially symmetric equivalents of 3D rf ion traps. SIT geometry of dimensions equivalent to the CIT0 are taken and field and multipoles are studied in it. Then optimization is applied to create a CIT geometry equivalent to the SIT under study. Axial field and ion trajectory was compared and observed to be matching. Finally, stability plot was generated for both SIT and its equivalent CIT and was found to present a close match. Chapter 4 presents the numerical results obtained for three-dimensional rf ion trap equivalent of CIT. In this chapter, we have considered two standard geometries, the CIT0 and the CITopt. Optimization was applied to create SIT geometries equivalent to the CIT0 and the CITopt respectively. Comparison of fields and ion trajectory confirmed the fact that non-axially symmetric traps can be created equivalent to any axially symmetric ion trap. We have also considered another case of axially symmetric circular planar ion trap which has an annular ring electrode and two planar endcap electrodes. Square equivalent of circular planar trap was created by the optimizer and its equivalent was verified by ion trajectory comparison. Chapter 5 summarizes the thesis with a few concluding remarks.

This thesis investigates the loss of high mass ions due to the initial thermal energy in ion trap mass analyzers. It provides an analytical expression for estimating the percentage loss of ions of a given mass at a particular temperature, in a trap operating with a set of conditions. The investigations have been carried out on quadrupole and cylindrical ion trap geometries. The three-dimensional Maxwellian velocity distribution function has been assumed to derive an expression for the percentage of ions lost. Adopting an approximation based on the observed escape velocity profiles of ions, an expression for the percentage loss of ions of a given mass has been derived as a function of the temperature for an ensemble of ions, its mass and its escape velocity. An analytical expression for the escape velocity has also been developed. It is seen that the escape velocity is a function of the trapping field, drive frequency and ion mass. Because the trapping field is determined by trap design parameters and operating conditions, it has been possible to study the influence of these parameters on ion loss. The parameters investigated include ion temperature, magnitude of the initial potential applied to the ring electrode (which determines the low mass cut-off), trap size, dimensions of apertures in the endcap electrodes and RF drive frequency. The studies demonstrate that ion loss due to initial thermal energy increases with increase in mass and that ion escape occurs in the radial direction. Reduction in the loss of high mass ions is favoured by lower ion temperatures, increasing low mass cut-off, increasing trap size, and higher RF drive frequencies. The dimensions of the apertures in the endcap electrodes do not influence ion loss in the range of aperture sizes considered.

Axially symmetric rf ion traps consists of a mass analyser having three electrodes, one of which is a central ring electrode and the other two are endcap electrodes. In the ideal Paul trap mass spectrometer, the electrodes have hyperboloidal shape (March and Hughes, 1989) and in mass analyser with simplified geometry, such as the cylindrical ion trap (Wu et al.,2005) the central electrode is a cylinder and the two endcap electrode and flat plates. rf-only or rf/dc potential is applied across the ring electrode and the grounded endcap electrodes for conducting the basic experiments of the mass spectrometer. In recent times, the miniaturisation of ion trap is one of the research interests in the field of mass spectrometry. The miniaturisation has the advantages of compactness, low power consumption and portability. However, this is achieved at the cost of the overall performance of the mass spectrometer with its deleterious effect on resolution. Research groups study the field distribution in the trap for better understanding of ion dynamics in the direction of achieving improved performance with the miniaturised traps. One aspect which has not received any attention in research associated with quadrupole ion traps is the possible role of the magnetic field in improving performance of these traps. Since in the quadrupole ion trap mass analyser ion is confined by an oscillating (rf) field, magnetic fields have been considered superfluous. The motivation of the thesis is to understand the dynamics of ions in axially symmetric rf ion traps, in the presence of the magnetic field. The axially symmetric rf ion trap geometries considered in this thesis are the Paul trap and the cylindrical ion trap (CIT). The changes incurred to the ion motion and Mathieu stability diagram in the presence of magnetic field is observed in this work. Also, the relation between the magnetic field and the Mathieu parameter is shown. The thesis contains 4 chapters: Chapter 1 provides the basic back ground of mass spectrometry and the operating principles. The equations of ion motion in the Paul trap is derived and also the solution to Mathieu equation is provided. The solution to the Mathieu equation are the Mathieu parameters and , when plotted with on the x-axis and on the y-axis, results in the Mathieu stability plot, the explanation of which is also given in the chapter. A brief description of the secular frequency associated with the ion dynamics is given in this chapter. The popular experiments conducted (i.e. the mass selective boundary ejection and resonance ejection) with a mass spectrometer is described here. Finally at the end of the chapter is the scope of the thesis. Chapter 2 facilitates with the preliminary study required fort he accomplishment of the task. The Paul trap and the CIT are the rf ion traps considered in this work. The geometries of these two traps are described in this chapter. The computational methods used for the analysis of various aspects of mass spectrometer is introduced. The computational methods used involve the methods used for calculating the charge distribution on the electrodes, potentials, multipole co-efficients and trajectory calculations. The boundary element method(BEM), calculation for Potentials and the Runge-Kutta method used for the trajectory calculations are introduced in this chapter. The expressions for calculating the multipole co-efficients are also specified. Chapter 3 presents the results obtained. The equations of ion motion in a quadrupole ion trap in the presence of magnetic field is derived here. Verification of numerical results with and without the magnetic field are presented at the end of this chapter. The chapter also presents various graphs showing the impact of magnetic field on the ion dynamics in the Paul trap and the CIT. The impact of the presence of magnetic field on the micro motion in -, -and -directions of the rf ion traps are shown in this chapter. Also the figures showing the variation in the Mathieu stability plots, with varying magnetic field intensity are presented in the chapter. At the end of this chapter the relation between the magnetic field and the Mathieu parameter is derived and plotted. Chapter 4 explains the various observations made from the results obtained. This chapter also highlights the future scope of the work for making this a more applicable one. References in the text have been given by quoting the author’s name and year of publication. Full references have been provide, in an alphabetic order, at the end of the thesis.