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Physical Review A

Hyperfine frequency shift and Zeeman relaxation in alkali-metal-vapor cells with antirelaxation alkene coating

Eric Corsini, Todor S. Karaulanov, M. V. Balabas, Dmitry Budker

Published Feb 14, 2013• 41 citations
Publisher

Abstract

An alkene-based antirelaxation coating for alkali-metal vapor cells exhibiting Zeeman relaxation times up to 77 s was recently identified by Balabas et al. The long relaxation times, two orders of magnitude longer than in paraffin- (alkane-) coated cells, motivate revisiting the question of what the mechanism is underlying wall-collision-induced relaxation and renew interest in applications of alkali-metal vapor cells to secondary frequency standards. We measure the width and frequency shift of the ground-state hyperfine $m{}_{F}=0\ensuremath{\rightarrow}m{}_{F}^{\ensuremath{'}}=0$ transition (clock resonance) in vapor cells with ${}^{85}$Rb and ${}^{87}$Rb atoms, with an alkene antirelaxation coating. We find that the frequency shift is slightly larger than for paraffin-coated cells and that the Zeeman linewidth scales linearly with the hyperfine frequency shift.

DOI
10.1103/physreva.87.022901

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The study of wall interactions of spin polarized rubidium atoms using the frequency shift in the electron paramagnetic resonance of the rubidium atoms

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I studied the effect of wall collisions on the electron paramagnetic resonance (EPR) of gas phase alkali metal atoms (87Rb). Two types of walls were studied: antirelaxation-coated walls and RbH-coated walls. I measured the dwell times of spin polarized Rb atoms on the two most common antirelaxation coatings, octadecyltrichlorosilane (OTS)- and paraffin. I found that at a cell temperature of 72 C the dwell times for OTS- and paraffin-coated walls are 0.9 ± 0.1 μs and 1.8 ± 0.2 μs, respectively. The implication of these dwell times, which are much longer than what was previously reported in the literature, is discussed in connection with the relaxing property of these coatings. In cells coated with RbH salt I made the first observation of the EPR frequency shift of the gas phase 87Rb atoms. Due to collisions with the RbH salt, which was nuclear spin polarized by spin exchange with optically pumped Rb vapor. The measured EPR frequency shifts are of the order of several hundred Hz in a millimeter-sized cell. By measuring the dependence of the EPR frequency shifts on cell length and by comparing the EPR frequency shifts in RbH-coated cells with those in OTS-coated cells, I provided convincing evidence that the observed EPR frequency shifts are due to collisions with RbH-coated walls, and not due to gas phase processes. The EPR frequency shift is due to the Fermi contact interaction between the s-electron of the adsorbed 87Rb atom and the polarized nucleus on the salt surface. The measured EPR frequency shifts allowed me to calculate the ensemble-averaged phase shift experienced by the Rb atom while adsorbed on the walls. Under our experimental condition this is about 70 mrad. My experiment opens up the possibility of studying surface NMR using gas phase EPR. The phase shift is proportional to the surface nuclear polarization, thus provides an interesting method for measuring the surface nuclear polarization using gas phase EPR. My observation will alert the high precision miniature atomic magnetometry community that collisions with cell walls may cause a systematic error and line broadening in the magnetic resonance frequency.

•Jan 1, 2014•0 citations
An alkene-based antirelaxation coating for alkali-metal vapor cells exhibiting Zeeman relaxation times up to 77 s was recently identified by Balabas et al. The long relaxation times, two orders of magnitude longer than in paraffin- (alkane-) coated cells, motivate revisiting the question of what the mechanism is underlying wall-collision-induced relaxation and renew interest in applications of alkali-metal vapor cells to secondary frequency standards. We measure the width and frequency shift of the ground-state hyperfine mF=0\ensuremath→mF\ensuremath′=0m{}_{F}=0\ensuremath{\rightarrow}m{}_{F}^{\ensuremath{'}}=0mF​=0\ensuremath→mF\ensuremath′​=0 transition (clock resonance) in vapor cells with 85{}^{85}85Rb and 87{}^{87}87Rb atoms, with an alkene antirelaxation coating. We find that the frequency shift is slightly larger than for paraffin-coated cells and that the Zeeman linewidth scales linearly with the hyperfine frequency shift.
Using laser optical pumping, widths and frequency shifts are determined for microwave transitions between ground-state hyperfine components of 85Rb^{85}\mathrm{Rb}85Rb and 87Rb^{87}\mathrm{Rb}87Rb atoms contained in vapor cells with alkane antirelaxation coatings. The results are compared with data on Zeeman relaxation obtained in nonlinear magneto-optical rotation experiments, a comparison important for quantitative understanding of spin-relaxation mechanisms in coated cells. By comparing cells manufactured over a $40\text{\penalty1000-\hskip0pt}\text{year}$ period we demonstrate the long-term stability of coated cells, an important property for atomic clocks and magnetometers.
Nonlinear magneto-optical Faraday rotation (NMOR) on the potassium D1 and D2 lines was used to study Zeeman relaxation rates in an antirelaxation paraffin-coated $3\text{\ensuremath{-}}\mathrm{cm}$-diameter potassium vapor cell. Intrinsic Zeeman relaxation rates of ${\ensuremath{\gamma}}^{NMOR}∕2\ensuremath{\pi}=2.0(6)\phantom{\rule{0.3em}{0ex}}\mathrm{Hz}$ were observed. The relatively small hyperfine intervals in potassium lead to significant differences in NMOR in potassium compared to rubidium and cesium. Using laser optical pumping, widths and frequency shifts were also determined for transitions between ground-state hyperfine sublevels of 39K^{39}\mathrm{K}39K atoms contained in the same paraffin-coated cell. The intrinsic hyperfine relaxation rate of ${\ensuremath{\gamma}}_{\mathit{expt}}^{\mathit{hf}}∕2\ensuremath{\pi}=10.6(7)\phantom{\rule{0.3em}{0ex}}\mathrm{Hz}$ and a shift of $\ensuremath{-}9.1(2)\phantom{\rule{0.3em}{0ex}}\mathrm{Hz}$ were observed. These results show that adiabatic relaxation gives only a small contribution to the overall hyperfine relaxation in the case of potassium, and the relaxation is dominated by other mechanisms similar to those observed in previous studies with rubidium.
Using laser optical pumping, widths and frequency shifts are determined for microwave transitions between ground-state hyperfine components of {sup 85}Rb and {sup 87}Rb atoms contained in vapor cells with alkane anti-relaxation coatings. The results are compared with data on Zeeman relaxation obtained in nonlinear magneto-optical rotation (NMOR) experiments, a comparison important for quantitative understanding of spin-relaxation mechanisms in coated cells. By comparing cells manufactured over a forty-year period we demonstrate the long-term stability of coated cells, an important property for atomic clocks and magnetometers.
I studied the effect of wall collisions on the electron paramagnetic resonance (EPR) of gas phase alkali metal atoms (87Rb). Two types of walls were studied: antirelaxation-coated walls and RbH-coated walls. I measured the dwell times of spin polarized Rb atoms on the two most common antirelaxation coatings, octadecyltrichlorosilane (OTS)- and paraffin. I found that at a cell temperature of 72 C the dwell times for OTS- and paraffin-coated walls are 0.9 ± 0.1 μs and 1.8 ± 0.2 μs, respectively. The implication of these dwell times, which are much longer than what was previously reported in the literature, is discussed in connection with the relaxing property of these coatings. In cells coated with RbH salt I made the first observation of the EPR frequency shift of the gas phase 87Rb atoms. Due to collisions with the RbH salt, which was nuclear spin polarized by spin exchange with optically pumped Rb vapor. The measured EPR frequency shifts are of the order of several hundred Hz in a millimeter-sized cell. By measuring the dependence of the EPR frequency shifts on cell length and by comparing the EPR frequency shifts in RbH-coated cells with those in OTS-coated cells, I provided convincing evidence that the observed EPR frequency shifts are due to collisions with RbH-coated walls, and not due to gas phase processes. The EPR frequency shift is due to the Fermi contact interaction between the s-electron of the adsorbed 87Rb atom and the polarized nucleus on the salt surface. The measured EPR frequency shifts allowed me to calculate the ensemble-averaged phase shift experienced by the Rb atom while adsorbed on the walls. Under our experimental condition this is about 70 mrad. My experiment opens up the possibility of studying surface NMR using gas phase EPR. The phase shift is proportional to the surface nuclear polarization, thus provides an interesting method for measuring the surface nuclear polarization using gas phase EPR. My observation will alert the high precision miniature atomic magnetometry community that collisions with cell walls may cause a systematic error and line broadening in the magnetic resonance frequency.