The precise measurement of transition frequencies in cold, trapped molecules has applications in fundamental physics, and extremely high accuracies are desirable. We determine suitable candidates by considering the simplest molecules with a single electron, for which the external-field shift corrections can be calculated theoretically with high precision. Our calculations show that H(2)(+) exhibits particular transitions whose fractional systematic uncertainties may be reduced to 5×10(-17) at room temperature. We also generalize the method of composite frequencies, introducing tailored linear combinations of individual transition frequencies that are free of the major systematic shifts, independent of the strength of the external perturbing fields. By applying this technique, the uncertainty of the composite frequency is reduced compared to what is achievable with a single transition, e.g., to the 10(-18) range for HD(+). Thus, these molecules are of metrological relevance for future studies.

High-precision laser spectroscopy of ultracold hydrogen molecular ions has the potential of improving the precision of the electron-to-proton mass ratio. An accurate knowledge of the spin structure of the transition is required in order to permit precise comparison with experimental transition frequencies. We calculate with a relative accuracy of the order of O(alpha2) the hyperfine splitting of the rovibrational states of HD+ with orbital momentum L

We analyse the effects of an external magnetic field on the ro-vibrational, rotational and radiofrequency transitions of the HD + molecular ion-an important systematic effect in precision spectroscopy of HD + , which is of interest for metrology of the fundamental constants. The effects of an external magnetic field on the ro-vibrational, rotational and radiofrequency (hyperfine) transitions of the HD + molecular ion are considered, for one-photon and, where relevant, two-photon transitions. The hyperfine structure of the spectrum lines is taken into account. Particular attention has been devoted to those transitions which are most insensitive to the magnetic field and its orientation with respect to the polarization of the radiation field. We identify experimentally accessible two-photon transitions that exhibit no Zeeman shift, one-photon and two-photon transitions that provide symmetrically split doublets, and one-photon transitions that show only a very weak quadratic Zeeman shift. The importance of the spin-stretched states is emphasized. The results can be used to determine the most suitable transitions given the experimental conditions.

The density shift and broadening of the transition lines of antiprotonic helium have been evaluated in the impact approximation using an interatomic potential calculated ab initio with the symmetry-adapted perturbation theory. The results help to remove an uncertainty of up to 10 ppm in the laser spectroscopy data on antiprotonic helium and are of importance in experimental tests of bound state QED and CPT invariance.

While measurements of the hyperfine structure of hydrogen-like atoms are traditionally regarded as test of bound-state QED, we assume that theoretical QED predictions are accurate and discuss the information about the electromagnetic structure of protons that could be extracted from the experimental values of the ground state hyperfine splitting in hydrogen and muonic hydrogen.Using recent theoretical results on the proton polarizability effects and the experimental hydrogen hyperfine splitting we obtain for the Zemach radius of the proton the value 1.040(16) fm. We compare it to the various theoretical estimates the uncertainty of which is shown to be larger that 0.016 fm. This point of view gives quite convincing arguments in support of projects to measure the hyperfine splitting of muonic hydrogen.