Polarization effects in gases are investigated by two methods of coherent spectroscopy - stimulated photon echo in molecular gas and laser-induced fluorescence in atomic vapour. A well developed photon echo experimental technique permitted us not only to measure relaxation rates of population, orientation and alignment on degenerated resonant levels in molecular gas but also to study their dependence on particles' longitudinal velocity. The degree of polarization of laser-induced fluorescence in Yb vapour in a mixture with Xe proves a large contribution of depolarizing collisions. The complicated non-exponential fluorescence decay at higher Yb pressures is explained by the radiation trapping.
The effect of translational velocity of active atoms and molecules on the properties of photon echo is investigated using the technique of coherent transient processes. A variation in the photon-echo decay with a frequency detuning of the excitation radiation relative to the center of the vibrational-rotational transition 0 ↔ 1 ν3 R(4, 3) is observed in a mixture of 13CH3F with atomic buffers. The results are interpreted using the dependence of the echo decay rate on the magnitude of the translational velocity of active particles. The dependence of the relaxation matrix on the direction of the velocity of active atoms results in a new phenomenon of the collision-induced echo, which is investigated at the transition 0 ↔ 1 174Yb in mixtures with atomic buffers.
Method of stimulated photon echo with specially chosen linear polarizations of exciting pulses of coherent resonant radiation is applied for investigation of collisional decay of orientation and alignment in molecular gas SF6 and its mixtures with buffers He and Xe. These relaxation rates are measured as a function of longitudinal velocities. Within experiment accuracy, no remarkable velocity dependence of depolarizing collisions rates was detected. This result confirms conventional approach of depolarizing collisions theoretical treatment.
A stimulated photon echo technique with specially selected linear polarizations of the coherent resonant driver pulses is used to study depolarizing collisions in the molecular gas SF 6 and in mixtures of it with buffer He and Xe. The collisional decay rates of the population, orientation, and alignment in an ensemble of gas particles are determined for the first time in a single experiment. These relaxation rates are measured as a function of the longitudinal translational velocities of the resonant particles. To within the experimental accuracy, no significant dependence of the collisional decay rates on the translational velocities of the particles was observed. This result confirms the conventional theoretical approach to depolarizing collisions. In pure SF 6 the decay rates for the orientation and alignment were lower than the relaxation constant for collisions involving a change in the longitudinal velocity (elastic collisions) that is known from experimental observations of the ordinary photon echo. This means that only some of the elastic collisions participate in destroying the multipole moments of the levels. Evidence is found that the relaxation of the multipole moments created by polarized radiation in a resonant medium of molecular SF 6 gas depends on j , the total angular momentum of the level.
Precise knowledge of collisional relaxation channels is in close relation with the research of both specific features of interaction potential and details of lineshape. When using nonlinear laser technique of spectral domain, it’s not so easy to distinguish between different channels of relaxation because of their integral contribution to the lineshape of rarefied gas. This report intends to demonstrate ability of coherent transient phenomena to overcome this difficulty. Comparative study of several photon echo modifications, performed in molecular gas SF6 has permitted to choose definite type of coherent transient phenomena, which is the most sensitive to peculiar channel of collisional relaxation. The data on relaxation rates of rotationally inelastic, elastic small angle scattering and depolarizing collisions in SF6 and its mixtures with buffer gases are examined.
It has been shown recently that molecular gas samples excited with coherent light can display a variety of transient phenomena, similar to those found in nuclear magnetic resonance. This article elucidates how these coherence effects can be used to isolate or unfold molecular collision mechanisms that normally remain hidden within the optical line shape. Elastic collisions, for example, are easily detected here in two-pulse photon echo experiments for a
13CH3F vibration-rotation transition. The echo-decay function which provides a signature for the velocity-changing collision diffusion mechanism, is not just a simple exponential in time but exhibits an $\mathrm{exp}(\ensuremath{-}K{t}^{3})$ contribution for short times and an $\mathrm{exp}(\ensuremath{-}\ensuremath{\Gamma}t)$ decay for long times. This behavior, which is unknown heretofore, contrasts with spin echoes in molecular liquids where Brownian motion leads only to the cubic decay law. An $\mathrm{exp}(\ensuremath{-}K{t}^{3})$ behavior can be understood in terms of a solution of the Fokker-Planck equation which describes the effect of Brownian motion on echo decay. Such a treatment is valid for small phase excursions; in the case of a gas, this implies the Doppler phase factor $k\ensuremath{\Delta}u\ensuremath{\tau}\ensuremath{\ll}1$, where $\stackrel{\ensuremath{\rightarrow}}{\mathrm{k}}$ is the propagation vector of light, $\ensuremath{\Delta}u$ is a characteristic velocity jump for a binary collision, and $\ensuremath{\tau}$ is the echo-pulse delay time. When $k\ensuremath{\Delta}u\ensuremath{\tau}\ensuremath{\gg}1$ as in the long-time regime, the Fokker-Planck solution fails. We, therefore, present a new solution to the Boltzmann transport equation using a weak collision model and find agreement with the entire echo time dependence observed. The echo measurements indicate very small changes in longitudinal velocity per
13CH3F-
13CH3F collision, i.e., $\ensuremath{\Delta}u=85$ cm/sec, thereby justifying the weak-collision model. The total elastic collision cross section is 430
A˚2. It follows that elastic collisions lead to velocity thermalization in a time of \ensuremath{\sim}5 sec when the
13CH3F pressure is 1 mTorr. A comparison is also made of the
13CH3F dephasing time ${\ensuremath{\tau}}_{2}$ in a coherent Raman beat decay, which is independent of velocity-changing collisions, with the longitudinal decay time
T1. Here,
T1 represents the molecule-optical interaction time, due largely to jumps in molecular rotation (
J) and orientation (
M) state, and is obtained from a delayed nutation measurement. The fact that the pressure dependent part of ${\ensuremath{\tau}}_{2}={T}_{1}$ shows that
T1 is also independent of velocity diffusion. Futhermore, when a hole is burned in the Doppler distribution, population recovery must be due to inelastic rather than elastic collisions. Optical Carr-Purcell echoes, multiple pulse echoes, provide a direct measure of the
13CH3F transverse dephasing time
T2 without the effect of elastic collisions while being sensitive to "phase interrupting collisions." Again, we find that
T2=T1 so that phase interruptions are negligible. Had such a process dominated the two-pulse echo, an $\mathrm{exp}(\ensuremath{-}\frac{t}{{T}_{2}})$ damping would have been noticed with no $\mathrm{exp}(\ensuremath{-}K{t}^{3})$ contribution. Thus, the present study covers several new aspects of molecular collisions. It represents the first detailed examination of velocity-changing collisions by coherence methods and without the complication of Doppler broadening.