The hyperfine structure of the 62P1/2 and 72P1/2 state of85Rb and87Rb and of the 62P3/2 state of87Rb has been investigated with optical double resonance at intermediate magnetic fields. The magnetic interaction constants,gj factors and lifetimes are: $$\begin{gathered} 6^2 P_{1/2} state: A\left( {^{85} Rb} \right) = 39.11\left( 3 \right) MHz,A\left( {^{87} Rb} \right) = 132.56 \left( 3 \right)MHz, \hfill \\ g_j = 0.6659\left( 3 \right), \tau = 1.14\left( {13} \right) \cdot 10^{ - 7} \sec , \hfill \\ 7^2 P_{1/2} state: A\left( {^{85} Rb} \right) = 17.68\left( 8 \right)MHz,A\left( {^{87} Rb} \right) = 59.92\left( 9 \right)MHz, \hfill \\ g_j = 0.6655\left( 5 \right), \hfill \\ 6^2 P_{3/2} state: g_j = 1.3337\left( {10} \right), \tau = 1.12\left( 8 \right) \cdot 10^{ - 7} \sec for ^{87} Rb. \hfill \\ \end{gathered} $$ From the hfs coupling constants of then2P multiplets a 11.5% core polarization contribution to the magnetic hfs of then2P3/2 states is obtained, which is found to be independent from the main quantum numbern. The expectation values j for thenp valence electrons corrected for core polarization are compared with those derived from the2P fine structure separation. Good agreement is achieved for allnp levels with the choice ofZi=Z−3=34 for the effective nuclear charge number. The nuclear quadrupole moments of85Rb and87Rb are rederived on the basis of this more improved treatment for thep-electron-nucleus interaction yielding $$\begin{gathered} Q_N \left( {^{85} Rb} \right) = + 0.274\left( 2 \right) \cdot 10^{ - 24} cm^2 \hfill \\ Q_N \left( {^{85} Rb} \right) = + 0.132\left( 1 \right) \cdot 10^{ - 24} cm^2 \hfill \\ \end{gathered} $$ where the error does not include the remaining theoretical uncertainty of about 10%.
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