Abstract A numerical approach that employs a multi‐level dressed state method to determine the AC‐Stark shifts of molecular rotational energy levels is described. This approach goes beyond the two‐level approximation often employed for simpler molecules, such as ammonia and acetonitrile, and is applicable to a variety of molecules. The calculations are used to develop experiments aimed at focusing, guiding, decelerating and trapping neutral, polyatomic, asymmetric‐top molecules by using microwave fields. Herein, numerical calculations are performed for acetonitrile and 4‐aminobenzonitrile. Based on these results, trajectory simulations are performed to predict the outcome of microwave focusing experiments in the TE1,1,p mode of a cylindrically symmetric microwave resonator. Simulations show that, for such an experimental setup, microwave focusing and guiding of 4‐aminobenzonitrile requires starting longitudinal velocities close to, or below, 100 m s−1, that is, much lower than values obtained with standard molecular beam techniques, such as supersonic expansion. Therefore, alternative beam‐generation techniques, for example, buffer‐gas‐cooled molecular beams, are required to extend microwave manipulation methods to larger and more complex molecules.
Abstract A numerical approach that employs a multi‐level dressed state method to determine the AC‐Stark shifts of molecular rotational energy levels is described. This approach goes beyond the two‐level approximation often employed for simpler molecules, such as ammonia and acetonitrile, and is applicable to a variety of molecules. The calculations are used to develop experiments aimed at focusing, guiding, decelerating and trapping neutral, polyatomic, asymmetric‐top molecules by using microwave fields. Herein, numerical calculations are performed for acetonitrile and 4‐aminobenzonitrile. Based on these results, trajectory simulations are performed to predict the outcome of microwave focusing experiments in the TE1,1,p mode of a cylindrically symmetric microwave resonator. Simulations show that, for such an experimental setup, microwave focusing and guiding of 4‐aminobenzonitrile requires starting longitudinal velocities close to, or below, 100 m s−1, that is, much lower than values obtained with standard molecular beam techniques, such as supersonic expansion. Therefore, alternative beam‐generation techniques, for example, buffer‐gas‐cooled molecular beams, are required to extend microwave manipulation methods to larger and more complex molecules.
Cold molecules are unique samples that can be exploited for a broad set of novel experiments, such as cold collision studies and precision spectroscopy. An important remaining challenge in this field is a widely applicable method to manipulate the motion of neutral polar molecules in high-field-seeking states, i.e., the molecular ground state and states of more complex medium- sized and large molecules. For molecules in these states, true three- dimensional field maxima in free space are required, which are an inherent property of electromagnetic waves. The experiments presented in this thesis exploit the interaction of polar molecules with near-resonant microwave fields in open Fabry–Pérot type resonators and in closed cylindrically symmetric resonators. Ammonia (14NH3) was chosen as a prototypical test molecule for these microwave manipulation experiments because well-controlled ammonia packets can be generated using Stark deceleration in single quantum states. These packets are ideal starting points for developing and characterizing novel motion manipulation techniques. In particular, the rovibronic ground state of para-ammonia has a strong interaction with microwave radiation close to 23.7 GHz corresponding to a wavelength of 12.7 mm. In a first set of experiments, transverse focusing of packets of ammonia molecules with mean forward velocities ranging from 20 m/s to 50 m/s was demonstrated in a closed cylindrically symmetric resonator. The resonator mode used for these experiments features an electric field maximum on the resonator axis that coincides with the molecular beam axis. In order to also manipulate the forward motion of the molecular packets, several consecutive electric field maxima on the molecular beam axis are required and the microwave field has to be rapidly switched at the appropriate times. In a modified closed cylindrically symmetric resonator with twelve consecutive electric field maxima on the axis, the first microwave guiding with full phase-space control was demonstrated for packets of ammonia molecules with a mean forward velocity ranging from 12 m/s to 25 m/s. With the same setup, also the first microwave acceleration and deceleration were accomplished with an extraction of as much as 30% of the initial kinetic energy and a gain by up to 60%. The main advantage of the microwave manipulation technique is its applicability to larger molecules that cannot be manipulated with conventional methods, such as Stark-deceleration. Successful deceleration is complicated for a number of reasons. For example, these larger molecules generally carry much higher kinetic energy. Furthermore, a precise theoretical calculation of the interaction with microwave fields becomes much more challenging. In the last part of this thesis, methods are proposed to increase the performance of the microwave decelerator, developed and characterized in this thesis, to eventually provide slow samples of medium-sized molecules, such as aminobenzonitrile, and trap ammonia.
Microwave radiation coupled into a cylindrically symmetric resonator is used to focus, guide, decelerate, and accelerate ammonia molecules in high-field-seeking states. In a first series of measurements, we demonstrate that the focal length of a microwave lens is directly proportional to the molecules’ velocity and to the inverse of the fourth root of the microwave power. In a second series of measurements employing a modified set-up, we use a multi-stage decelerator exploiting the TE1,1,12 mode of a cylindrical resonator and various switching schemes. We can deliberately choose between spatial focusing and velocity focusing while guiding, and we demonstrate kinetic energy reduction by as much as 30% of a 12 m/s slow packet of molecules utilising the 12 deceleration stages.
The main contribution of this project to the field of cold and ultracold molecules is we firstly demonstrated successful manipulation of the motion of polyatomic molecular beam in the rotational ground state, which has the lowest temperature of all possible states. Chapter 1 gives a summary of this field, including the application of cold and ultracold molecules, the methods to obtain them, and each method’s advantages and disadvantages. Once we decelerate molecular ensembles, we would like to trap the cold and ultracold molecules in electric trap, megnetic trap and megneto-optical trap. Chapter 2 starts with an introduction of the concept of supersonic beam and the basic knowledge of it, such as the specific features. The experimental setup will also be presented and explained in this chapter. The main highlight of this project is that we are manipulating molecules in the real ground state. Our molecular source is a Counter Rotating Nozzle(CRN), which can precool (or slow in alternate terminology) molecules in all states including the rotational ground state. The principle and performance of CRN will be presented and explained in Chapter 3. After obtaining a well precooled molecular beam, the microwave lens effect on various species is presented in Chapter 4. Meanwhile, the principle of AC Stark shift, AC dipole force and the microwave standing wave modes, such as TE modes and TM modes, will be explained in this chapter as well. Finally, I’ll summarize, draw conclusion of this work and describe the future expectation of this project in Chapter 5.
Cold molecules are unique samples that can be exploited for a broad set of novel experiments, such as cold collision studies and precision spectroscopy. An important remaining challenge in this field is a widely applicable method to manipulate the motion of neutral polar molecules in high-field-seeking states, i.e., the molecular ground state and states of more complex medium-sized and large molecules. For molecules in these states, true three-dimensional field maxima in free space are required, which are an inherent property of electromagnetic waves. The experiments presented in this thesis exploit the interaction of polar molecules with near-resonant microwave fields in open Fabry–Pérot type resonators and in closed cylindrically symmetric resonators. Ammonia (14NH3) was chosen as a prototypical test molecule for these microwave manipulation experiments because well-controlled ammonia packets can be generated using Stark deceleration in single quantum states. These packets are ideal starting points for developing and characterizing novel motion manipulation techniques. In particular, the rovibronic ground state of para-ammonia has a strong interaction with microwave radiation close to 23.7 GHz corresponding to a wavelength of 12.7 mm. In a first set of experiments, transverse focusing of packets of ammonia molecules with mean forward velocities ranging from 20 m/s to 50 m/s was demonstrated in a closed cylindrically symmetric resonator. The resonator mode used for these experiments features an electric field maximum on the resonator axis that coincides with the molecular beam axis. In order to also manipulate the forward motion of the molecular packets, several consecutive electric field maxima on the molecular beam axis are required and the microwave field has to be rapidly switched at the appropriate times. In a modified closed cylindrically symmetric resonator with twelve consecutive electric field maxima on the axis, the first microwave guiding with full phase-space control was demonstrated for packets of ammonia molecules with a mean forward velocity ranging from 12 m/s to 25 m/s. With the same setup, also the first microwave acceleration and deceleration were accomplished with an extraction of as much as 30% of the initial kinetic energy and a gain by up to 60%. The main advantage of the microwave manipulation technique is its applicability to larger molecules that cannot be manipulated with conventional methods, such as Stark-deceleration. Successful deceleration is complicated for a number of reasons. For example, these larger molecules generally carry much higher kinetic energy. Furthermore, a precise theoretical calculation of the interaction with microwave fields becomes much more challenging. In the last part of this thesis, methods are proposed to increase the performance of the microwave decelerator, developed and characterized in this thesis, to eventually provide slow samples of medium-sized molecules, such as aminobenzonitrile, and trap ammonia.
Abstract Manipulating the motion of large polyatomic molecules, such as benzonitrile (C6H5CN), presents significant difficulties compared to the manipulation of diatomic molecules. Although recent impressive results have demonstrated manipulation, trapping, and cooling of molecules as large as CH3F, no general technique for trapping such molecules has been demonstrated, and cold neutral molecules larger than 5 atoms have not been trapped (M. Zeppenfeld, B. G. U. Englert, R. Glöckner, A. Prehn, M. Mielenz, C. Sommer, L. D. van Buuren, M. Motsch, G. Rempe, Nature 2012, 491, 570–573 ). In particular, extending Stark deceleration and electrostatic trapping to such species remains challenging. Here, we propose to combine a novel “asymmetric doublet state” Stark decelerator with recently demonstrated slow, cold, buffer‐gas‐cooled beams of closed‐shell volatile molecules to realize a general system for decelerating and trapping samples of a broad range of volatile neutral polar prolate asymmetric top molecules. The technique is applicable to most stable volatile molecules in the 100–500 AMU range, and would be capable of producing trapped samples in a single rotational state and at a motional temperature of hundreds of mK. Such samples would immediately allow for spectroscopy of unprecedented resolution, and extensions would allow for further cooling and direct observation of slow intramolecular processes such as vibrational relaxation and Hertz‐level tunneling dynamics.
We have focused and decelerated benzonitrile (C7H5N) molecules from a molecular beam, using an array of time-varying inhomogeneous electric fields in alternating-gradient configuration. Benzonitrile is prototypical for large asymmetric top molecules that exhibit rich rotational structure and a high density of states. At the rotational temperature of 3.5K in the pulsed molecular beam, many rotational states are populated. Benzonitrile molecules in their absolute ground state are decelerated from 320to289m∕s, and similar changes in velocity are obtained for excited rotational states. All measurements agree well with the outcome of trajectory calculations. These experiments demonstrate that such large polyatomic molecules are amenable to the powerful method of Stark deceleration.