Controlling the Motion of Rydberg Molecules in Inhomogeneous Electric Field

Y. Yamakita, R. Takahashi, N. Hori, and K. Ohno

Department of Chemistry, Graduate School of Science, Tohoku University

Controlling the translational motion of atoms and molecules, particularlly cooling and trapping of molecules, is an interesting subject for study in chemical physics. The experimental approaches employed for such studies include (a) photoassociation of alkali atoms trapped at ultra-low temperatures, (b) He buffer gas cooling and magnetic trapping of paramagnetic molecules, and (c) deceleration of polar molecules using fast-switched electric fields. Our approach is primarily an application of method (c) to high-n Rydberg states, which is based on a similar principle to that of the Stern-Gerlach experiment. Since the Rydberg states give rise to large energy shifts (Stark effect) in electric fields, non-polar molecules or atoms can be controlled by inhomogeneous electric fields of moderate strength (F1000 V/cm). This Rydberg-Stark deceleration scheme has been indeed demonstrated for Rydberg H2 molecules [1] and Ar atoms [2], and simulated to produce a bunch of cold molecules resting at mean zero velocity [3,4]. In this talk we summarize spectroscopic measurements for such a purpose on the He atom in triplet Rydberg states with principal and magnetic quantum numbers n15 and |m|=0,1 respectively [5]. The Stark effect in He has been extensively studied for more than 50 years by numerous early studies [6-8] and also by recent studies [9,10]. However, to our best knowledge, the available experimental data are limited to either a narrow range of large n values (n40) [7,8], or under specific experimental conditions such as field strength and tunablity of lasers [6]. Hence experimental data are desired in suitable ranges of n and F. Also simple theoretical calculations are of use for designing experiments rather than sophisticated theoretical treatments such as WKB-quantum defect theory [6,8]. We obtain an Stark map for a range of ca. 15n20 experimentally comparing with calculations by matrix diagonalization of effective Hamiltonian [7,11]. Experiments are performed with a cw metastable He atom discharge source [12]. A set of three fine grids are placed parallel in the excitation region. Grid 1 applies a homogeneous DC Stark field from 0 to -1600 V/cm. The metastable He(23S) atoms are then photo-excited to high Rydberg states by a UV pulsed laser in the presence of the field. Grid 2 applies an ionizing pulsed field of magnitude 6000 V/cm with respect to the voltage. It increases from 0 to 6000 V/cm in 150 ns with a delay time of 800 ns to the laser, keeps a constant voltage for 150 ns, and decreases in 150 ns. Spectra are recorded by monitoring the ions as a function of laser frequency. The laser frequency is resonant with an one-photon transition from the intermediate 23S state (159856.07760 cm-1 above the ground state) to the Rydberg series converging on the ionization threshold (IE=198310.7723 cm-1). The polarization of the laser can be set either parallel or perpendicular to the Stark field, which defines the space quantization axis z for the optically-allowed m=0 or |m|=1 states, respectively. Figures 1 (a),(b) presents the Stark effect in homogeneous electric fields of 0-1000 V/cm for the 1snp3P Rydberg series with m=0 and |m|=1 respectively. Comparisons between observed and calculated spectra indicate the experimental intensity distributions are in reasonable agreements with the calculated ones. This means that the transition intensities reflect predominantly the magnitude of mixing with the np states, and that are not affected

significant decay processes. The Stark manifolds display asymmetric distributions until they become nearly round hydrogenic manifolds. The lower-energy sub-levels have larger intensities than those at higher-energy sides. At field greater than 400 V/cm additional peaks are observed in the low-energy sides of the m=0 Stark manifolds (Figure 1(a)). These peaks originate from l=0 states which gain intensities through mixing with the l=1 states. This observation illustrates that the lower-sides of the Stark sub-levels, which are in general close to optically-allowed low-l states, tend to obtain larger transition probabilities.

Figure 1. Comparison between experimental and calculated Stark spectra of the n=16,17 Stark manifolds of the Rydberg states with (a) m=0 and (b) |m|=1 respectively. The simulation has been convoluted with a Gaussian laser bandwidth FWHM of 0.5 cm-1.

Energy shift and level mixing can be viewed more quantitatively as Stark maps (Figure 2). Avoided crossing are obtained, of which widths differ significantly between the m=0 and |m|=1 cases, as is commonly found for alkali-metal atoms. The width is larger in the m=0 case where the lobe of the electronic wavefunction of a Rydberg electron extends to the same z-direction, than in the m0 case in which there are degenerated wavefunctions of which Rydberg electron lobes pointing to various directions. The width is estimated to be 1 cm-1 and 0.3 cm-1 for both cases, respectively, at the first avoided crossing between n=15 and n=16 extreme states. When an ionizing field applied, a population in a sub-level traverses from the position of the Stark field towards the right-hand side of the figures where bound states couple to the continuum. It is commonly known that it goes adiabatically or diabatically depending on the slew rate of the ionizing pulsed field (and of course the width). The mechanism also determines the threshold for field ionization. If field ionization is adiabatic it proceeds along a zig-zag passage, and the threshold would be located approximately at the classical saddle point energy, 6.12F (cm-1), below the ionization energy, where F is given in V/cm. In the present case, the slew rate of the ionizing pulse is S=dF/dt=4.01010 Vcm-1s-1, and probability for the diabatic transition is calculated to be PD=1.910-13 for the |m|=1 case. Therefore diabatic traverse is highly unlikely for the m=0 and |m|=1 states, and excitation to Rydberg states should be made under the condition of no level crossings taking place. Now

we have obtained experimental Stark maps and can determine realistic experimental parameters for a Stark decelerator. Simulations based on the Stark control indicate that the complete deceleration can be realized by using time-varying inhomogeneous electric fields for a supersonic beam with a reduced initial velocity.

Figure 2. Stark map calculated for the Rydberg states. (a) The m=0 Rydberg states are field ionized above the classical saddle point energy (solid line) through the adiabatic zig-zag passage. (b) The saddle point energy for the |m|=1 Rydberg states are lifted by the centrifugal barrier (solid line).

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