We investigate the excitation of the 5D_{5/2} level in Rb atoms using counter-propagating laser beams, which are nearly resonant to the one-photon 5S_{1/2} - 5P_{3/2} and 5P_{3/2} - 5D_{5/2} transitions, ensuring that a sum of the optical frequencies corresponds to the 5S_{1/2} - 5D_{5/2} transition. The excitation produced by two-photon and step-wise processes is detected via spontaneously emitted fluorescence at 420 nm arising from the 6P_{3/2} - 5S_{1/2} transition. The dependences of blue fluorescence intensity on atomic density and laser detuning from the intermediate 5P_{3/2} level have been investigated. The sensitivity of the frequency detuned bi-chromatic scheme for atom detection has been estimated. A novel method for sum frequency stabilization of two free-running lasers has been suggested and implemented using two-photon Doppler-free fluorescence and polarization resonances.
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