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Spectrochimica Acta Part B Atomic Spectroscopy

A novel and efficient excitation- and ionization-scheme for laser resonance ionization of mercury

Alexey A Podshivalov, Oleg I. Matveev, Benjamin W. Smith, James D. Winefordner

Published Dec 1, 1999• 8 citations
Publisher
DOI
10.1016/s0584-8547(99)00112-3

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Excitation of sodium by excited and by ionized mercury vapor.---The excitation of the sodium spectrum by ionized mercury distilling from an arc was studied in a tube in which conditions were under control. An auxiliary electrode in the stream of mercury vapor was used to increase the number of excited atoms at the point of observation until the excitation due to them predominated over that due to the ions. The spectrum produced by excited mercury atoms was thus compared with that due to mercury ions. The spectrum due to the excited atoms showed the marked "resonance" effect shown earlier by Beutler and Josephy. The spectrum due to mercury ions also showed excitation corresponding to the excitation energy of the metastable mercury atom. This may be accounted for as due to metastable atoms formed as the result of recombination of mercury ions. An alternative explanation is that the excitation of a sodium atom by a mercury ion is by a three body impact involving a mercury ion, a sodium atom and an electron. This was suggested by the fact that when sodium is introduced into the ionized mercury there is a strong enhancement of the mercury lines originating at the two $3S$ levels, which seems to be best explained as due to three body impacts. It seems probable that both this and the above process are of the same nature. It was noted further that the spectrum excited by ionized mercury resembles the chemiluminescence spectrum resulting from mixing sodium and mercuric chloride vapors. The spark line of mercury 3984, not previously found in the luminous mercury stream, was found when sodium was present.

Physical Review•Mar 1, 1929•5 citations
The polarization dependences of some resonant multiphoton ionizations in atomic mercury have been measured with a broadband (bandwidth ≈ 1.5 cm−1) multimode dye laser at moderate light intensities (≈ 500 MW∙cm−2). The multiphoton processes studied were the absorption of four photons to a resonant 1S0, 1D2, or 3D2 level by one-photon ionization. Complete saturation of the one-photon ionization step results in the ionization of all atoms excited to the resonant level. Because of the saturation of the ionization step, the polarization dependence of the four-photon excitation to the resonant level is measured. The theory developed by Dalby et al. is shown to give good agreement with the experiment when it is used to calculate the polarization dependence of the multiphoton transition to the resonant level. For the 6d1D2 resonance, distortions in the polarization dependence and an unusual linewidth dependence on the light polarization were observed. We relate these observations to the alternating current Stark effect and to the production of the third harmonic of the laser light in the focal volume.
Excitation of sodium by excited and by ionized mercury vapor.---The excitation of the sodium spectrum by ionized mercury distilling from an arc was studied in a tube in which conditions were under control. An auxiliary electrode in the stream of mercury vapor was used to increase the number of excited atoms at the point of observation until the excitation due to them predominated over that due to the ions. The spectrum produced by excited mercury atoms was thus compared with that due to mercury ions. The spectrum due to the excited atoms showed the marked "resonance" effect shown earlier by Beutler and Josephy. The spectrum due to mercury ions also showed excitation corresponding to the excitation energy of the metastable mercury atom. This may be accounted for as due to metastable atoms formed as the result of recombination of mercury ions. An alternative explanation is that the excitation of a sodium atom by a mercury ion is by a three body impact involving a mercury ion, a sodium atom and an electron. This was suggested by the fact that when sodium is introduced into the ionized mercury there is a strong enhancement of the mercury lines originating at the two 3S3S3S levels, which seems to be best explained as due to three body impacts. It seems probable that both this and the above process are of the same nature. It was noted further that the spectrum excited by ionized mercury resembles the chemiluminescence spectrum resulting from mixing sodium and mercuric chloride vapors. The spark line of mercury 3984, not previously found in the luminous mercury stream, was found when sodium was present.