Cryogenic buffer gas cells have been a workhorse for the cooling of molecules in the last decades. The straightforward sympathetic cooling principle makes them applicable to a huge variety of different species. Notwithstanding this success, detailed simulations of buffer gas cells are rare, and have never been compared to experimental data in the regime of low to intermediate buffer gas densities. Here, we present a numerical approach based on a trajectory analysis, with molecules performing a random walk in the cell due to collisions with a homogeneous buffer gas. This method can reproduce experimental flux and velocity distributions of molecules emerging from the buffer gas cell for varying buffer gas densities. This includes the strong decrease in molecule output from the cell for increasing buffer gas density and the so-called boosting effect, when molecules are accelerated by buffer-gas atoms after leaving the cell. The simulations provide various insights which could substantially improve buffer-gas cell design.
We report an experimental investigation on the Doppler-free saturated absorption spectroscopy of buffer-gas-cooled Barium monofluoride (BaF) molecules in a 4~K cryogenic cell. The obtained spectra with a resolution of 19~MHz, much smaller than previously observed in absorption spectroscopy, clearly resolve the hyperfine transitions. Moreover, we use these high-resolution spectra to fit the hyperfine splittings of excited $A(v=0)$ state and find the hyperfine splitting of the laser-cooling-relevant $A^2Π_{1/2}(v=0, J=1/2, +)$ state is about 18 MHz, much higher than the previous theoretically pr…
For over five decades, studies in the field of chemical physics and physical chemistry have primarily aimed to understand the quantum properties of molecules. However, high-resolution rovibronic spectroscopy has been limited to relatively small and simple systems because translationally and rotationally cold samples have not been prepared in sufficiently large quantities for large and complex systems. In this study, we present high-resolution rovibronic spectroscopy results for large gas-phase molecules, namely, free-base phthalocyanine (FBPc). The findings suggest that buffer-gas cooling may …
We report direct laser cooling of a symmetric top molecule, reducing the transverse temperature of a beam of calcium monomethoxide (CaOCH$_3$) to $1.8\pm0.7$ mK while addressing two distinct nuclear spin isomers. These results open a path to efficient production of ultracold chiral molecules and conclusively demonstrate that by using proper rovibronic optical transitions, both photon cycling and laser cooling of complex molecules can be as efficient as for much simpler linear species.
Cryogenic buffer gas beams are central to many cold molecule experiments. Here, we use absorption and fluorescence spectroscopy to directly compare molecular beams of AlF, CaF, MgF, and YbF molecules, produced by chemical reaction of laser ablated atoms with fluorine rich reagents. The beam brightness for AlF is measured as $2\times 10^{12}$ molecules per steradian per pulse in a single rotational state, comparable to an Al atomic beam produced in the same setup. The CaF, MgF and YbF beams show an order of magnitude lower brightness than AlF, and far below the brightness of Ca and Yb beams. Th…
Over the past decade, tremendous progress has been made to extend the tools of laser cooling and trapping to molecules. Those same tools have recently been applied to polyatomic molecules (molecules containing three or more atoms). In this review, we discuss the scientific drive to bring larger molecules to ultralow temperatures, the features of molecular structure that provide the most promising molecules for this pursuit, and some technical aspects of how lasers can be used to control the motion and quantum states of polyatomic molecules. We also present opportunities for and challenges to t…
We present a practical roadmap to achieve optical cycling and laser cooling of asymmetric top molecules (ATMs). Our theoretical analysis describes how reduced molecular symmetry, as compared to diatomic and symmetric non-linear molecules, plays a role in photon scattering. We present methods to circumvent limitations on rapid photon cycling in these systems. We calculate vibrational branching ratios for a diverse set of asymmetric top molecules and find that many species within a broad class of molecules can be effectively cooled with a manageable number of lasers. We also describe methods to …
We report a generally applicable computational and experimental approach to determine vibronic branching ratios in linear polyatomic molecules to the $10^{-5}$ level, including for nominally symmetry forbidden transitions. These methods are demonstrated in CaOH and YbOH, showing approximately two orders of magnitude improved sensitivity compared with the previous state of the art. Knowledge of branching ratios at this level is needed for the successful deep laser cooling of a broad range of molecular species.
The YbF molecule is a sensitive system for measuring the electron's electric dipole moment. The precision of this measurement can be improved by direct laser cooling of the molecules to ultracold temperature. However, low-lying electronic states arising from excitation of a 4f electron may hinder laser cooling. One set of these "4f hole" states lies below the $A^2Π_{1/2}$ excited state used for laser cooling, and radiative decay to these intermediate levels, even with branching ratios as small as $10^{-5}$, can be a hindrance. Other 4f hole states lie very close to the $A^2Π_{1/2}$ state, and …
We have designed, constructed, and commissioned a cryogenic helium buffer-gas source for producing a cryogenially-cooled molecular beam and evaluated the effect of different cell geometries on the intensity of the produced molecular beam, using ammonia as a test molecule. Planar and conical entrance and exit geometries are tested. We observe a three fold enhancement in the NH$_3$ signal for a cell with planar-entrance and conical-exit geometry, compared to that for a typically used `box'-like geometry with planar entrance and exit. These observations are rationalized by flow-field simulations …
We report on a scheme for laser cooling of $^{12}$C$_2$. We have calculated the branching ratios for cycling and repumping transitions and calculated the number of photon scatterings required to achieve deflection and laser cooling of a beam of $C_2$ molecules under realistic experimental conditions. Our results demonstrate that C$_2$ cooling using the Swan ($d^3Π_\text{g} \leftrightarrow a^3Π_\text{u}$) and Duck ($d^3Π_\text{g} \leftrightarrow c^3Σ_\text{u}^+$) bands is achievable via techniques similar to state-of-the-art molecular cooling experiments. The Phillips ($A^1Π_\text{u} \leftright…
The cryogenic buffer gas beam (CBGB) is an important tool in the study of cold and ultracold molecules. While there are known techniques to enhance desired beam properties, such as high flux, low velocity, or reduced divergence, they have generally not undergone detailed numerical optimization. Numerical simulation of buffer gas beams is challenging, as the relevant dynamics occur in regions where the density varies by orders of magnitude, rendering standard numerical methods unreliable or intractable. Here, we present a hybrid approach to simulating CBGBs that combines gas dynamics methods wi…
Kinetic modeling of molecular beam formation in a cryogenic buffer-gas cell
Vienna Center for Quantum Science and Technology, Atominstitut, TU Wien（维也纳量子科学与技术中心，原子研究所，维也纳工业大学）；LSS, Faculty of Engineering, Friedrich-Alexander-Universität Erlangen-Nürnberg（埃尔朗根-纽伦堡大学工程学院）；Institute of Space Systems, University of Stuttgart（斯图加特大学空间系统研究所）
We explore the suitability of ultracold collisions between spin-polarized SrF($^2Σ^+$) molecules and Rb($^2$S) atoms as elementary steps for the sympathetic cooling of SrF($^2Σ^+$) molecules in a magnetic trap. To this end, we carry out quantum mechanical scattering calculations on ultracold Rb+SrF collisions in a magnetic field based on an accurate potential energy surface for the triplet electronic state of Rb-SrF developed ab initio using a spin-restricted coupler cluster method with single, double and noniterative triple excitations [RCCSD(T)]. The Rb-SrF interaction has a global minimum w…
We demonstrate optical cycling and sub-Doppler laser cooling of a cryogenic buffer-gas beam of calcium monohydride (CaH) molecules. We measure vibrational branching ratios for laser cooling transitions for both excited electronic states A and B. We measure further that repeated photon scattering via the $A\leftarrow X$ transition is achievable at a rate of $\sim$ $1.6\times10^6$ photons/s and demonstrate the interaction-time limited scattering of $\sim$ $200$ photons by repumping the largest vibrational decay channel. We also demonstrate the ability to sub-Doppler cool a molecular beam of CaH …
Optical cycling transitions and direct laser cooling have recently been demonstrated for a number of alkaline-earth dimers and trimer molecules. This is made possible by diagonal Franck-Condon factors between the vibrational modes of the optical transition. Achieving a similar degree of cooling to micro-Kelvin equivalent kinetic energy for larger polyatomic molecules, however, remains challenging. Since polyatomic molecules are characterized by multiple degrees of freedom and have a correspondingly more complex structure, it is far from obvious whether there exist polyatomic molecules that can…
In this work, we show that van der Waals molecules X-RG (where RG is the rare gas atom) may be created through direct three-body recombination collisions, i.e., X + RG + RG $\rightarrow$ X-RG + RG. In particular, the three-body recombination rate at temperatures relevant for buffer gas cell experiments is calculated via a classical trajectory method in hyperspherical coordinates [J. Chem. Phys. 140, 044307 (2014)]. As a result, it is found that the formation of van der Waals molecules in buffer gas cells (1 K $\lesssim T \lesssim 10$ K) is dominated by the long-range tail (distances larger tha…
Rapid and repeated photon cycling has enabled precision metrology and the development of quantum information systems using a variety of atoms and simple molecules. Extending optical cycling to structurally complex molecules would provide new capabilities in these areas, as well as in ultracold chemistry. Increased molecular complexity, however, makes realizing closed optical transitions more difficult. Building on the already established strong optical cycling of diatomic, linear triatomic, and symmetric top molecules, recent theoretical and experimental work has indicated that cycling will be…
Ultracold collisions of the polyatomic species CaOH are considered, in internal states where the collisions should be dominated by long-range dipole-dipole interactions. The computed rate constants suggest that evaporative cooling can be quite efficient for these species, provided they start at temperatures achievable by laser cooling. The rate constants are shown to become more favorable for evaporative cooling as the electric field increases. Moreover, long-range dimer states (CaOH)$^*_2$ are predicated to occur, having lifetimes on the order of microseconds.
Slow, Continuous Beams of Large Gas Phase Molecules
冷，连续，高通量束的苯甲腈，氟苯，和苯甲醚已经创建。用低温气体的缓冲气体冷却提供了冷却和缓慢的向前射束速度。苯甲腈束被测量为具有峰值为67 $\pm 5$ m s $^{-1}$的前向速度，以及$10^{15}$分子s $^{-1}$的连续通量。这些光束为高分辨率光谱学提供了一个连续的光源，并为进一步空间操纵这些分子提供了一个有吸引力的起点，包括最终的捕获。
Context. Evaporative (sublimation) cooling of icy interstellar grains occurs when the grains have been suddenly heated by a cosmic-ray (CR) particle or other process. It results in thermal desorption of icy species, affecting the chemical composition of interstellar clouds. Aims. We investigate details on sublimation cooling, obtaining necessary knowledge before this process is considered in astrochemical models. Methods. We employed a numerical code that describes the sublimation of molecules from an icy grain, layer by layer, also considering a limited diffusion of bulk-ice molecules toward …
