The resonance broadening of the sodium D-lines in absorption was determined by measuring the contour of the line wings directly. The vapor pressures of sodium ranged from 10-3 to 75 mm Hg, with negligible amount of foreign gases. Over nearly the entire range, the half-intensity width varied linearly with the density of the absorbing atoms; i.e. Δν1/2/N = 0.78 x 10-7 sec-1cm3 --the constant being about twice that predicted by Houston, but much less than the experimental result by Hughes and LLoyd. Above 5 mm pressure, the half-intensity width appeared to increase slightly faster than N. Somewhat in contradiction to theory, the relative width, Δν1/2,s/Δν1/2,1' was 1.16. The natural width measured was, within experimental error, consistent with previous values. The inverse square contour for the absorption coefficient was satisfactory up to 5 mm Hg; beyond this pressure an inverse cube contour fitted better. No definite evidence of van der Waal force was observed at high pressures; likewise, no appreciable shifts and asymmetries. MgO windows were used and the temperature determination was made reliable.
By direct measurement of the contours of the line wings, the resonance broadening of the sodium
D lines in absorption was determined for vapor pressures of sodium ranging from ${10}^{\ensuremath{-}3}$ to 70 mm Hg with negligible amount of foreign gases. Over nearly the entire range, the half-intensity width varied linearly with the density of the absorbing atoms; i.e., $\frac{\ensuremath{\Delta}{\ensuremath{\nu}}_{\frac{1}{2}}}{N}=0.80\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}7}$ ${\mathrm{sec}.}^{\ensuremath{-}1}$ ${\mathrm{cm}}^{\ensuremath{-}3}$---the constant being 1.6 times that predicted by theory but much less than the corresponding experimental results for potassium. Above 5 mm pressure, $\ensuremath{\Delta}{\ensuremath{\nu}}_{\frac{1}{2}}$ increased slightly faster than
N; moreover, the contour for the absorption coefficient was more adequately represented by an inverse cube contour than by the inverse square. Somewhat in contradiction to theory, the relative width, $\frac{\ensuremath{\Delta}{\ensuremath{\nu}}_{\frac{1}{2},8}}{\ensuremath{\Delta}{\ensuremath{\nu}}_{\frac{1}{2},l}}$ was 1.12. No definite evidence of van der Waals force was observed at the higher pressures; likewise no appreciable shifts or asymmetries. The natural width measured was consistent with previous results.
Selective reflection from sodium, potassium, rubidium, and caesium vapors in the neighborhood of the resonance lines was observed for vapor pressures between 10 mm. and 1 atm., using a steel tube with a window of transparent magnesium oxide. Reflecting power as a function of frequency was measured by using incident light of continuous spectral distribution. The reflection contour for pressures up to ½ atm. is in good agreement with the theory of reflection from an absorbing medium. For each line the damping constant in the dispersion equations varies as the square root of the number of atoms per cubic centimeter, as was found previously for mercury and cadmium. For the two members of the resonance doublet the damping constants are proportional to the square roots of the oscillator strengths. In a region about 5 cm.−1 wide about each resonance frequency the reflected intensity measured experimentally is greater than that calculated. These lines of residual intensity may be due to a second kind of selective reflection. At pressures above ½ atm. the observed reflection contour cannot be explained by the simple anomalous dispersion theory.
The intensity ratio D2/D1 for the sodium doublet has been measured for radiation from excited sodium atoms which result from the optical dissociation of sodium iodide vapor by ultraviolet light in the 2082→2500 A region. With shorter wavelength ultraviolet light as exciting source, the D2/D1 ratio is 0.98 and increases to above 1.5 with longer exciting wavelengths. Addition of foreign gases cause the observed D2/D1 ratio to increase to 1.89 for large foreign gas pressure. Cross sections for the transfer of excited sodium atoms from the 32P32 to the 32P½ state and vice versa due to collisions with foreign molecules have been measured as they depend on the relative velocity between excited sodium atom and foreign molecule. The Doppler broadening of the separate D lines emitted in the atomic fluorescence of sodium iodide has been estimated from absorption measurements. Both lines show equal broadening within the experimental error of the observations. Measurements were made with a photomultiplier tube. The sodium doublet was resolved with a reflection grating monochromator.
Experimental line profiles and integrated intensities for backscattered and forward-scattered resonance radiation using white-light excitation are compared with theory for Na densities between
1019 and
1022 atoms/
m3. Absorption measurements are used to verify linewidth and line-wing asymmetry parameters and Na-vapor densities. The scattered spectral intensities are normalized to the incident flux using calibrated diffusers. Measurements of scattered intensities were also made as
N2 was added to the Na. The line profiles and integrated intensities were calculated using a model which assumes complete redistribution of the radiation scattered by an atom and takes into account both radiative and nonradiative transport of the resonance excitation. The theory includes the effects of quenching by
Na2 and by admixed
N2. With the white-light excitation used in these experiments the radiative transport is found to dominate the nonradiative transport except at wavelengths very near line center. The agreement between experimental and theoretical line profiles is good at high sodium densities (\ensuremath{\sim} 5 \ifmmode\times\else\texttimes\fi{}
1021 atoms/
m3) where instrumental resolution is not a serious limitation. The agreement between experimental and theoretical integrated intensities is within experimental error for Na densities of (1-10) \ifmmode\times\else\texttimes\fi{}
1019 and (2-5) \ifmmode\times\else\texttimes\fi{}
1021 atoms/
m3. At the intermediate densities the approximately 20% discrepancy may be caused by the incomplete redistribution of radiation in the scattering process.
Sodium vapor, in the density range
1013 to 5 \ifmmode\times\else\texttimes\fi{}
1014 ${\mathrm{cm}}^{\ensuremath{-}3}$, was excited by a cw dye laser, tuned 20-150 GHz from either the
D1 or
D2 resonance line. We observed a three-peak scattered spectrum, consisting of the Rayleigh component at the laser frequency, and the two fluorescence components (direct and sensitized) at the atomic resonance-line frequencies. Corrections to the Rayleigh signals for anisotropy and polarization effects, and to the fluorescence signals for radiation trapping, were made in order to obtain the ratio of the sum of the total intensities of the two fluorescence components to that of the Rayleigh component. This ratio combined with a measurement of the line-wing absorption coefficient yields the sodium density and the
D-line self-broadening rate coefficients [${k}_{\mathrm{br}}=4.67\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}7}$
cm3${\mathrm{s}}^{\ensuremath{-}1}$ (\ifmmode\pm\else\textpm\fi{}15%) for the
D2 line and ${k}_{\mathrm{br}}=3.07\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}7}$
cm3${\mathrm{s}}^{\ensuremath{-}1}$ (\ifmmode\pm\else\textpm\fi{}15%) for the
D1 line]. Asymmetry in the self-broadened line wings due to fine-structure recoupling was observed. The measured intensity ratio of the
D lines, combined with pulsed measurements of the effective radiative decay rates in the presence of radiation trapping, yields the fine-structure collisional-mixing cross section [$\ensuremath{\sigma}(3{P}_{\frac{3}{2}}\ensuremath{\rightarrow}3{P}_{\frac{1}{2}})=172$
A˚2(\ifmmode\pm\else\textpm\fi{}18%)] at $T\ensuremath{\cong}300\ifmmode^\circ\else\textdegree\fi{}$ C. Our results are compared to other experiments and to theory.