A measurement of the 3P1 metastable state in Ca

Ryszard Drozdowski, Michalina Ignaciuk, Jerzy Kwela +1 more

Giovanni Giusfredi, P. Minguzzi, F. Strumia +1 more

F. Arbes, M. Benzing, Th. Gudjons +2 more

David Husain, Gareth O. Roberts

Two separate series of investigations have been carried out on the optically metastable states Ca[4s4p(3PJ)] and Ca[4s3d(1D2)], generated by pulsed dye-laser excitation at λ= 657.3 nm {Ca[4s4p(3P1)]â†� Ca[4s2(1S0)]} and λ= 457.5 nm {Ca[4s3d(1D2)]â†� Ca[4s2(1S0)]}, with particular emphasis on energy pooling. The kinetic behaviour of these two states has been characterised in detail across a wide range of temperature and pressure by time-resolved atomic emission measurements at the resonance wavelengths. In the case of Ca[4s3d(1D2)] these represent the first time-resolved measurements on this atomic state, yielding a mean radiative lifetime for emission to all lower states of τe= 1.71 ± 0.03 ms, in accord with time-of-flight measurements in atomic beams. The measured temperature dependence of the diffusion coefficient D12[Ca(4 1D2)–He], when expressed in the form D12∝Tn, yielded n= 1.77 ± 0.08. Further, the rate constant for the collisional quenching of Ca(4 1D2) by Ca(4 1S0) itself is estimated to be kCa=(4 ± 3)× 10–14 cm3 atom–1 s–1, in sensible accord with similar data for the quenching of Ca(4 3PJ) by the ground-state calcium atom. Energy pooling between Ca(4 3PJ)+ Ca(4 3PJ) is shown to give rise directly to Ca[4s4p(1P1)] and Ca[4s3d(1D2)]. Energy pooling between Ca(4 1D2)+ Ca(4 1D2) is shown to yield 22 electronic states, each of whose kinetic behaviour was characterised quantitatively from the relevant atomic emission profiles, including measurement of relative atomic yields.

David Husain, Gareth O. Roberts

We present a kinetic study of energy pooling in the equilibrium-coupled system: Ca[4s3d(1D2)]+ Mg[3s2(1S0)]⇌ Ca[4s2(1S0)]+ Mg[3s3p(3PJ)] following pulsed dye-laser excitation of both Mg(3PJ) and Ca(1D2) atoms at λ= 457.1 nm. [Mg(3P1)â†� Mg(1S0)] and λ= 457.5 nm [Ca(1D2)â†� Ca(1S0)] in the presence of helium across the temperature range 800–1100 K. Quantitative characterisation of decay profiles for Mg(3PJ) and Ca(1D2) by time-resolved emission measurements at the above wavelengths using boxcar integration indicates the effectively instantaneous establishment and maintenance of the near-resonant equilibrium under all conditions of temperature and pressure via the observed equality in the first-order decay coefficients for removal of both states. Energy pooling into some 16 higher-lying states of magnesium and calcium, including atomic levels close to the energetically accessible limit, were observed and their temporal behaviour characterised. With the exceptions of Mg[3s4s(3S1)] and Ca[4s4p(1P1)] atoms, all these pooled states exhibited first-order kinetic behaviour. Measured first-order decay coefficients for these pooled states were found to be always twice those of the energy store states, indicating their production via collisions involving the metastable states Mg(3PJ), Ca(1D2) and possibly Ca(3PJ). Initial relative populations of energy-pooled states were estimated in all cases and found to lie in the range 10–4–10–6, thus constituting a small ‘bleed-off’ from the and Ca(1D2) energy stores without disturbing the observed first-order decay of these two states in the equilibrium-coupled system.