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ChemPhysChem

Decelerating and Trapping Large Polar Molecules

David Patterson

Published Jul 25, 2016• 3 citations
Publisher

Abstract

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.

DOI
10.1002/cphc.201600517

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Molecules in the low temperature limit offer fascinating research perspectives in physics and chemistry, and molecule cooling and deceleration has developed into a research field of its own.The grand challenge today is to prepare dense samples with ample cold molecules.Towards this end, we present an elegant solution to this problem by a nonconventional approach, employing the centrifugal force in a rotating frame to decelerate molecules to a standstill.The centrifuge deceleration is a generic method since its principle is not associated with any specific internal structure of the molecules.Moreover, electrostatic guiding of molecules is applied throughout the deceleration process, which enables for the first time the deceleration of continuous molecular beams to achieve unprecedented high fluxes of slow molecules.In a proof-ofprinciple experiment, we demonstrate fluxes of ∼ 10 9 molecules/s and densities of ∼ 10 8 molecules/cm 3 below k B •1 K in the laboratory frame, originated from a roomtemperature effusive beam source.The efficiency of this decelerator is measured to be up to 20%, outperforming all the existing molecular deceleration methods.The generality of this method is demonstrated by the deceleration of several polyatomic molecular species, CH 3 F, CF 3 H, and CF 3 CCH.In addition to presenting the basic principle and the results, we also describe thoroughly in this thesis the design of the centrifuge decelerator, optimized through Monte-Carlo trajectory simulations, and the technical assembly.The second focus of this thesis is on the development and implementation of a simple and robust internal-state thermometry method for cold polyatomic molecules.The method is based on the combination of resonant radio-frequency depletion spectroscopy and Monte Carlo trajectory simulations.The radio-frequency depletion spectroscopy is capable of addressing 100% of the rotational states populated by the cold polyatomic molecules, as well as resolving their hyperfine states.With this tool, various aspects of cryogenic buffer-gas cooling used as a source of internally cold molecules are characterized.The properties of the cold molecular beams obtained at different buffer-gas temperature, densities, and cooling regimes, are analyzed.The cooling processes for different polyatomic molecules are compared.These studies reveal also two interesting phenomena in the buffer-gas cooling process.Firstly, evidence is provided that molecular rotational degrees of freedom can thermalize more efficiently than their translational ones.Secondly, the measurements provide indications for dependence of the collisional relaxation rate on the rotational states of the molecules.

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Research in the field of cold polar molecules is progressing rapidly. An array of interesting\ntopics is being developed including precision measurement and fundamental tests, quantum phase transitions, and ultracold chemistry. In particular, dipolar molecules in well-defined quantum states enable exquisite control of their interactions via applied electric fields. The long-range, anisotropic interaction between dipolar molecules leads to new collision dynamics that could be used for novel collective effects, quantum state engineering, and information processing. The focus of this Thesis is the production of cold samples of neutral OH molecules via Stark deceleration and magnetic trapping for novel collision experiments. This novelty results from our combination of cold external beams and trapped target molecules which facilitates observation of dipolar effects as well as low temperature collision resonances. The large permanent electric dipole moment of OH allows us to precisely tune the lab-frame velocity of the molecular packets from ∼ 500 m/s to rest. We have magnetically trapped OH packets at the terminus of our Stark decelerator at a temperature of 70 mK and density of 106 cm−3. With improved understanding of Stark deceleration, we optimize the decelerator efficiency and its coupling to the magnetic trap. Our latest trap design uses permanent ring magnets to create a three-dimensional magnetic quadrupole field. Use of magnetically trapped OH molecules for collision experiments with external beams allow us the unique opportunity of observing both elastic and inelastic collisions. In addition, the trap confinement yields sensitivity to differential elastic cross sections at low collision energies. This open magnetic trap has allowed measurement of collision cross sections between trapped OH and external supersonic beams of He and D2, the latter of which is of astrophysical interest due to the role of H2-OH collisions in pumping interstellar OH megamasers. The combination of trapped OH molecules and temperature tuned beams of He and D2 has facilitated measurement of the lowest-energy D2-OH collision cross sections yet reported. More recently, we report the first observation of electric-field dependent cross sections between two different species of cold polar molecules - OH and ND3 - thereby demonstrating control over molecular scattering in the cold regime. By combining for the first time the production techniques of Stark deceleration and buffer gas cooling, we increase the molecular interaction time by∼ 105 over traditional crossed-beam experiments to gain enhanced sensitivity at the characteristic densities of cold molecule production.

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Cold molecules

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Slowing, cooling, and trapping molecules One of the major achievements in physics during the last two decades of the twentieth century was the ability to cool and trap atoms [1]. Laser cooling can produce previously inconceivable atomic temperatures of less than 1 μK. Atoms with sufficiently low kinetic energy can be trapped in magnetic and optical traps and thus studied for a prolonged time, thereby improving the resolution of spectroscopy by many orders of magnitude as well as reducing Doppler broadening. Furthermore, besides the external degrees of freedom, the internal degrees of freedom of the atoms can also be manipulated, leading to full control of the atoms. One of the holy grails of physics, the achievement of Bose–Einstein condensation in a dilute gas, was achieved mainly because of laser cooling and trapping of atoms. One of the natural extensions of laser cooling and trapping of atoms is the application of the techniques to molecules. Molecules offer a much richer internal structure than atoms, and thus provide extended possibilities to experimentalists. However, atomic laser cooling is based on the repetitive scattering of light and requires a closed, or at least nearly closed, two-level system. Because of the complicated internal structure of molecules, a closed two-level system cannot usually be found because they have many different electronic, vibrational, and rotational states and in general can decay to many different states after absorption of light (see Chap. 16). This requires a complete rethinking of the schemes that are used to cool atoms. Still, because of the extended possibilities cold molecules can offer with respect to cold atoms, there have been a large number of techniques developed to slow, cool, and trap them. These techniques can be divided into two classes, namely direct and indirect cooling. In the first case, molecules at cryogenic or room temperature are directly slowed and cooled. Although many different slowing techniques are used, this chapter focuses on Stark slowing of molecules since it was the first technique developed. Apart from the Stark shift of the molecules, the Zeeman and light shift of molecules can also be used to slow them. The idea behind Stark slowing is to subject the moving molecules to a continuously increasing electric field so that their kinetic energy is converted into potential energy.

Cambridge University Press eBooks•Dec 31, 2015•0 citations
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.
Molecules in the low temperature limit offer fascinating research perspectives in physics and chemistry, and molecule cooling and deceleration has developed into a research field of its own.The grand challenge today is to prepare dense samples with ample cold molecules.Towards this end, we present an elegant solution to this problem by a nonconventional approach, employing the centrifugal force in a rotating frame to decelerate molecules to a standstill.The centrifuge deceleration is a generic method since its principle is not associated with any specific internal structure of the molecules.Moreover, electrostatic guiding of molecules is applied throughout the deceleration process, which enables for the first time the deceleration of continuous molecular beams to achieve unprecedented high fluxes of slow molecules.In a proof-ofprinciple experiment, we demonstrate fluxes of ∼ 10 9 molecules/s and densities of ∼ 10 8 molecules/cm 3 below k B •1 K in the laboratory frame, originated from a roomtemperature effusive beam source.The efficiency of this decelerator is measured to be up to 20%, outperforming all the existing molecular deceleration methods.The generality of this method is demonstrated by the deceleration of several polyatomic molecular species, CH 3 F, CF 3 H, and CF 3 CCH.In addition to presenting the basic principle and the results, we also describe thoroughly in this thesis the design of the centrifuge decelerator, optimized through Monte-Carlo trajectory simulations, and the technical assembly.The second focus of this thesis is on the development and implementation of a simple and robust internal-state thermometry method for cold polyatomic molecules.The method is based on the combination of resonant radio-frequency depletion spectroscopy and Monte Carlo trajectory simulations.The radio-frequency depletion spectroscopy is capable of addressing 100% of the rotational states populated by the cold polyatomic molecules, as well as resolving their hyperfine states.With this tool, various aspects of cryogenic buffer-gas cooling used as a source of internally cold molecules are characterized.The properties of the cold molecular beams obtained at different buffer-gas temperature, densities, and cooling regimes, are analyzed.The cooling processes for different polyatomic molecules are compared.These studies reveal also two interesting phenomena in the buffer-gas cooling process.Firstly, evidence is provided that molecular rotational degrees of freedom can thermalize more efficiently than their translational ones.Secondly, the measurements provide indications for dependence of the collisional relaxation rate on the rotational states of the molecules.
We report on the electrostatic trapping of neutral SrF molecules. The molecules are captured from a cryogenic buffer-gas beam source into the moving traps of a 4.5-m-long traveling-wave Stark decelerator. The SrF molecules in X^{2}Σ^{+}(v=0,N=1) state are brought to rest as the velocity of the moving traps is gradually reduced from 190 m/s to zero. The molecules are held for up to 50 ms in multiple electric traps of the decelerator. The trapped packets have a volume (FWHM) of 1 mm^{3} and a velocity spread of 5(1) m/s, which corresponds to a temperature of 60(20) mK. Our result demonstrates a factor 3 increase in the molecular mass that has been Stark decelerated and trapped. Heavy molecules (mass>100 amu) offer a highly increased sensitivity to probe physics beyond the standard model. This work significantly extends the species of neutral molecules of which slow beams can be created for collision studies, precision measurement, and trapping experiments.
Slowing down atoms using laser cooling, together with techniques like magnetic trapping and evaporative cooling, has led to numerous exciting results over the last decade [1], with the realization of Bose-Einstein condensation as the most spectacular achievement [2]. Laser-cooling schemes are applicable to atoms since closed multilevel systems can be realized and many consecutive absorptionemission cycles can be induced. This leads to a significant momentum transfer from the photons of the laser to the atom, resulting in a change of the velocity of the atom. There currently is a great interest in producing cold molecules for the study of cold molecule-molecule collisions, molecular quantum collective effects, Doppler-free spectroscopy, frequency standards, as well as many other applications already realized for atoms [3]. Slowing down of neutral molecules, a prerequisite for being able to trap them, has proven to be considerably more difficult to be achieved, however. The above-mentioned laser-cooling scheme cannot be applied to slow down molecules as no simple closed-level systems can be found; the unavoidable off-resonant radiative decay of molecules from the excited state to other vibrational levels in the electronic ground state hampers efficient momentum transfer [4]. Once molecules are present at sufficiently low kinetic energies, below a fraction of a cm21, they can be trapped in various ways. Trapping of neutral molecules in inhomogeneous magnetic [3] and electric fields [5] and trapping based on the use of evanescent fields close to the dielectricvacuum interface have been proposed [6]. It has also been suggested that extremely high laser powers might be used to induce a dipole moment in polarizable molecules, leading to trapping of these molecules in the laser beam [7]. Other methods to produce slow molecules have been put forward and have recently been successfully applied to produce the first samples of trapped molecules. By injecting molecules in a cold buffer gas, sufficiently low kinetic energies of the injected molecules can be obtained after thermalization that they can subsequently be trapped in an inhomogeneous magnetic field. This has recently been demonstrated for CaH injected in 3He buffer gas at temperatures of around 0.3 K [8]. Associative collisions between ultracold trapped atoms [9] have proven to be
The large electric dipole moments associated with highly excited Rydberg states of atoms and molecules make gas-phase samples in these states very well suited to deceleration and trapping using inhomogeneous electric fields. The methods of Rydberg-Stark deceleration with which this can be achieved are reviewed here. Using these techniques, the longitudinal motion of beams of atoms and molecules moving at speeds as high as 2500 m/s have been manipulated, with changes in kinetic energy of up to |Δ E kin|=1.3×10−20 J (|Δ E kin|/e=80 meV or |Δ E kin|/h c=650 cm −1) achieved, while decelerated and trapped samples with number densities of 106– 107 cm −3 and translational temperatures of ∼150 mK have been prepared. Applications of these samples in areas of research at the interface between physics and physical chemistry are discussed.
Research in the field of cold polar molecules is progressing rapidly. An array of interesting\ntopics is being developed including precision measurement and fundamental tests, quantum phase transitions, and ultracold chemistry. In particular, dipolar molecules in well-defined quantum states enable exquisite control of their interactions via applied electric fields. The long-range, anisotropic interaction between dipolar molecules leads to new collision dynamics that could be used for novel collective effects, quantum state engineering, and information processing. The focus of this Thesis is the production of cold samples of neutral OH molecules via Stark deceleration and magnetic trapping for novel collision experiments. This novelty results from our combination of cold external beams and trapped target molecules which facilitates observation of dipolar effects as well as low temperature collision resonances. The large permanent electric dipole moment of OH allows us to precisely tune the lab-frame velocity of the molecular packets from ∼ 500 m/s to rest. We have magnetically trapped OH packets at the terminus of our Stark decelerator at a temperature of 70 mK and density of 106 cm−3. With improved understanding of Stark deceleration, we optimize the decelerator efficiency and its coupling to the magnetic trap. Our latest trap design uses permanent ring magnets to create a three-dimensional magnetic quadrupole field. Use of magnetically trapped OH molecules for collision experiments with external beams allow us the unique opportunity of observing both elastic and inelastic collisions. In addition, the trap confinement yields sensitivity to differential elastic cross sections at low collision energies. This open magnetic trap has allowed measurement of collision cross sections between trapped OH and external supersonic beams of He and D2, the latter of which is of astrophysical interest due to the role of H2-OH collisions in pumping interstellar OH megamasers. The combination of trapped OH molecules and temperature tuned beams of He and D2 has facilitated measurement of the lowest-energy D2-OH collision cross sections yet reported. More recently, we report the first observation of electric-field dependent cross sections between two different species of cold polar molecules - OH and ND3 - thereby demonstrating control over molecular scattering in the cold regime. By combining for the first time the production techniques of Stark deceleration and buffer gas cooling, we increase the molecular interaction time by∼ 105 over traditional crossed-beam experiments to gain enhanced sensitivity at the characteristic densities of cold molecule production.
Slowing, cooling, and trapping molecules One of the major achievements in physics during the last two decades of the twentieth century was the ability to cool and trap atoms [1]. Laser cooling can produce previously inconceivable atomic temperatures of less than 1 μK. Atoms with sufficiently low kinetic energy can be trapped in magnetic and optical traps and thus studied for a prolonged time, thereby improving the resolution of spectroscopy by many orders of magnitude as well as reducing Doppler broadening. Furthermore, besides the external degrees of freedom, the internal degrees of freedom of the atoms can also be manipulated, leading to full control of the atoms. One of the holy grails of physics, the achievement of Bose–Einstein condensation in a dilute gas, was achieved mainly because of laser cooling and trapping of atoms. One of the natural extensions of laser cooling and trapping of atoms is the application of the techniques to molecules. Molecules offer a much richer internal structure than atoms, and thus provide extended possibilities to experimentalists. However, atomic laser cooling is based on the repetitive scattering of light and requires a closed, or at least nearly closed, two-level system. Because of the complicated internal structure of molecules, a closed two-level system cannot usually be found because they have many different electronic, vibrational, and rotational states and in general can decay to many different states after absorption of light (see Chap. 16). This requires a complete rethinking of the schemes that are used to cool atoms. Still, because of the extended possibilities cold molecules can offer with respect to cold atoms, there have been a large number of techniques developed to slow, cool, and trap them. These techniques can be divided into two classes, namely direct and indirect cooling. In the first case, molecules at cryogenic or room temperature are directly slowed and cooled. Although many different slowing techniques are used, this chapter focuses on Stark slowing of molecules since it was the first technique developed. Apart from the Stark shift of the molecules, the Zeeman and light shift of molecules can also be used to slow them. The idea behind Stark slowing is to subject the moving molecules to a continuously increasing electric field so that their kinetic energy is converted into potential energy.