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The influence of pulse repetition rate of a femtosecond Ti:Sa laser (800 nm, 45 fs, 0.82 mJ) on intensity of spectral lines at optical breakdown on the surface of CaCl2 water solution is experimentally determined. It is demonstrated that, with increasing pulse repetition rate from 20 to 1000 Hz, the intensity of Ca II (393.3 nm) emission line reduces by 44%, while the plasma continuum remains unchanged within measurement error.

The electron-impact excitation-rate constants for atoms and ions in the ground state have been calculated. It is shows that, using data on the excitation-rate constants, it is possible to compare the limits of detection of the corresponding elements in femtosecond laser-induced breakdown spectroscopy.

The fraction of focused femtosecond laser radiation energy absorbed by a laser-induced spark in air has been studied. It is established that the absorbed energy exhibits nonlinear growth with increasing energy of the laser pulse. The threshold power for laser-induced spark formation in air is 5.2 GW.

The influence of the diameter of the beam of a femtosecond Ti:Sapphire laser (800 nm, 40 fs, 0.8 mJ) on the intensity of spectral lines upon optical breakdown on the surface of CaCl2 aqueous solution has been determined experimentally. It is shown that an increase in the laser-beam diameter from 7 to 14 mm on a focusing lens for identical pulse energy increases the intensities of the CaII (393.3 nm) and Hα (656 nm) lines by factors of 3 and 20, respectively. This effect can be used to increase the intensities of emission lines of chemical elements in femtosecond laser-induced breakdown spectroscopy of liquids and, accordingly, improve the sensitivity of this method.