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Register a new userH2+ and HD+: candidates for a molecular clock
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Authors
Jean-Philippe Karr
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We investigate the leading systematic effects in ro-vibrational spectroscopy of the molecular hydrogen ions H2+ and HD+, in order to assess their potential for the realization of optical clocks that would be sensitive to possible variations of the proton-to-electron mass ratio. Both two-photon (2E1) and quadrupole (E2) transitions are considered. In view of the weakness of these transitions, most attention is devoted to the light shift induced by the probe laser, which we express as a function of the transition amplitude, differential dynamic polarizability and clock interrogation times. Transition amplitudes and dynamic polarizabilites including the effect of hyperfine structure are then calculated in a full three-body approach to get a precise evaluation of the light shift. Together with the quadrupole and Zeeman shifts that are obtained from previous works, these results provide a realistic estimate of the achievable accuracy. We show that the lightshift is the main limiting factor in the case of two-photon transitions, both in H2+ and HD+, leading to expected accuracy levels close to 5 10-16 in the best cases. Quadrupole transitions have even more promising properties and may allow reaching or going beyond 10-16.
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Expectation values of the Breit operators and the $Q$ terms are calculated for HD$^+$ with the vibrational number $v=0-4$ and the total angular momentum $L=0-4$. Relativistic and radiative corrections to some ro-vibrational transition frequencies are determined. Numerical uncertainty in $R_{infty}alpha^2$ order correction is reduced to sub kHz or smaller. Our work provides an independent verification of Korobovs calculations [Phys. Rev. A {bf74}, 052506 (2006); {bf77}, 022509 (2008)].
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