The interaction of an intense optical-maser field with excited atoms in a gas discharge leads to a considerable change in the population of those levels which are resonant at the maser frequency. This will cause a change in the population of other levels that are connected to the maser levels through collision-induced nonradiative as well as radiative transitions. Using the 1.15-\ensuremath{\mu} optical maser, these effects have been studied in detail for the
2s levels of neon where the changes are completely due to collisions. By analyzing the intensity changes in spontaneous emission originating from a gas-discharge cell placed within the maser resonator, we have observed the approach to a partial thermalization of two closely spaced levels. In this way we have been able to obtain the atomic-collision cross section for excitation transfer between the
2s2 and
2s3 levels. In pure neon this has been found to be ${\ensuremath{\sigma}}_{23}=(2.3\ifmmode\pm\else\textpm\fi{}0.3)\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}16}$
cm2. For a helium-neon mixture the measured cross section is ${\ensuremath{\sigma}}_{23}=(1.8\ifmmode\pm\else\textpm\fi{}0.3)\ifmmode\times\else\texttimes\fi{}{10}^{\ensuremath{-}16}$
cm2. The experimental method used to determine these cross sections eliminates the uncertainties caused by the effects of electron-atom collisions and radiative cascade. These techniques also yield the ratio of the Einstein coefficients for the transitions $2{s}_{2}\ensuremath{\rightarrow}2{p}_{10}$ and $2{s}_{3}\ensuremath{\rightarrow}2{p}_{10}$. The measured ratio is $\frac{{A}_{2}}{{A}_{3}}=3.0\ifmmode\pm\else\textpm\fi{}0.4$.
A method for producing electronic-state coherences using either collisionally-aided radiative excitation (or "optical collision") or laser-induced collisional energy transfer (or "radiative collision") is proposed. Two atoms,
A and ${A}^{\ensuremath{'}}$, collide in the presence of two pulsed-laser fields having frequencies $\ensuremath{\Omega}$ and ${\ensuremath{\Omega}}_{1}$. It is shown that by choosing ${\ensuremath{\Omega}}_{1}\ifmmode\pm\else\textpm\fi{}\ensuremath{\Omega}$ such that an energy-conserving transition can occur in the composite $A{A}^{\ensuremath{'}}$ system, one can create an electronic-state coherence in the
A or ${A}^{\ensuremath{'}}$ atoms. The coherence can be produced between states of the same or of opposite parity; if it is between states of opposite parity, coherent emission at frequency ${\ensuremath{\Omega}}_{1}\ifmmode\pm\else\textpm\fi{}\ensuremath{\Omega}$ may be generated. The relationship of this work to theories of "pressure-induced extra resonances" in four-wave mixing is discussed.
The close-coupled theory of atomic collisions in the presence of a radiation field may be used to calculate the distribution of final atomic states which results from absorption of polarized light during a collision. The theory applies equally well to optical collisions (line broadening) and to radiative collisions (laser-induced collisional energy transfer). For an optical collision the detuning $\ensuremath{\omega}\ensuremath{-}{\ensuremath{\omega}}_{\ensuremath{\infty}}$ is restricted to be larger than either the Rabi frequency or the widths due to natural, Doppler, or pressure broadening. The radiation field is assumed to be weak enough that the transition probabilities are linear in field intensity. The molecular picture is emphasized in which the wave function is expanded in a basis of field-free molecular states and the Hamiltonian is blocked in accordance with molecular quantum numbers. The quantities needed to predict experimental observables are reduced radiative scattering
S-matrix elements ${s}_{\ensuremath{\omega}}$ in the asymptotic Hund's case-(e) representation. The theory of product orientation and alignment is equivalent to that which has been developed for molecular photodissociation. It requires coherent sums of ${s}_{\ensuremath{\omega}}$ matrix elements from different transition branches, that is, for
P-,
Q-, and
R-type transitions corresponding to changes of -1, 0, and +1 in total molecular angular momentum. On the other hand, the total absorption coefficient and the branching ratio to different final fine-structure states irrespective of orientation or alignment depend on incoherent sums of the same matrix elements.