New results are presented of an experimental investigation of the spectrum of 36P → 37P two-photon microwave transition in Rydberg atoms of sodium in a constant electric field. Depending on the conditions of excitation of the initial 36P state (the constant electric field is switched on either before or after the exciting laser pulse) and polarization of laser radiation, a strong variation is observed of the amplitudes of individual two-photon transitions between the fine-structure. Stark components of the 36P and 37P states. This effect is an analog of the Paschen-Back effect in a strong magnetic field and is due to the break of L-S coupling and to the variation of the wave functions of Rydberg electrons in an electric field. It is also found that the break of L-S coupling affects considerably the shape of double Stark resonance arising upon intersection of the virtual intermediate level. of two-photon transition with the real intermediate 37S level.
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