Coherent transients at dressed levels

Possibilities for the control of the parameters of free-polarization decay (FPD), optical nutation, and photon echo (PE) using the dressing field are studied. Coherent transients are generated with the Stark switching technique and are detected in the radiation of the probe field polarized orthogonally to the dressing field. The evolution-operator technique is employed in the calculations. The experiments are performed at the R(4, 3) transition of the 0 ? 1 v₃ ¹³CH₃F vibrational band with the radiation of a cw CO₂ laser. It is theoretically and experimentally demonstrated that FPD and PE are suppressed upon an increase in the intensity of the dressing field. The observed shapes of the transient FPD and PE signals and their variations with the dressing field intensity are in qualitative agreement with the results of the calculations.     

Unimolecular photochemistry of 4-thiouracils

Unimolecular phototautomeric reactions in 4-thiouracil, 1-methyl-4-thiouracil and 6-aza-4-thiouracil were studied using the matrix-isolation technique combined with infrared absorption spectroscopy. For monomers of these compounds, isolated in solid argon at 10 K, an intramolecular proton-transfer photoreaction was observed. Upon UV (lambda > 345 nm) irradiation, the initial oxo-thione forms of 4-thiouracils were converted into the corresponding oxo-thiol tautomers. The photogenerated oxo-thiol isomers were identified by comparing their experimental IR spectra with the spectra theoretically calculated at the DFT(B3LYP)/6-311++G(2d,p) level. Good agreement between the observed and predicted pattern of spectral bands allowed a reliable identification. This is the first report on experimental observation of isomeric forms of 4-thiouracils other than the canonical oxo-thione tautomers.     

Depolarizing collision anisotropy and collision echo in ytterbium vapor

A photon echo induced exclusively by collisions of ytterbium atoms with buffer gas atoms has been observed at a 0 ? 1-type¹ S ₀(6s ²)-³ P ₁(6s6p) ¹⁷⁴Yb transition. The polarization properties of a collision echo and the buffer gas density dependence of its intensity agree with theoretical predictions of a model of depolarizing collisions that takes into account the dependence of a relaxation matrix on the velocity of active particles. Thus, direct experimental evidence of the relaxation anisotropy due to depolarizing collisions has been obtained.     

Coherent transients in gases

A great variety of coherent transient processes in atomic and molecular gases is investigated. The degeneracy with respect to magnetic sublevels, which is typical of working levels of atomic and molecular transitions in gases, leads to new phenomena. In particular, the non-Faraday rotation of the coherent-response polarization vector at the 0 ↔ 1 transition is investigated in the presence of the longitudinal magnetic field in the ¹⁷⁴Yb vapor for both photon echo and stimulated photon echo. A specific relaxation channel that involves the depolarizing collisions emerges in a gas due to the degeneracy of working levels. Such collisions are especially important for atoms and are also observed in molecules. The anisotropy of the depolarizing collisions leads to a new phenomenon of the collision photon echo, which is experimentally demonstrated for the 0 ↔ 1 transition in the ¹⁷⁴Yb mixtures with atomic buffers. The velocity-dependent relaxation rates are observed for various coherent phenomena in molecular gases. The coherent control of a few coherent transient processes is implemented.     

Photon echo generated at the transition 0–1 in ytterbium vapor

Photon echo generated at the inter-combination transition (6s ²) ¹ S ₀ ? (6s6p) ³ P ₁ of ¹⁷⁴Yb was investigated for pure ytterbium vapor and for its mixtures with atomic buffers. In pure ytterbium vapor, the polarization of photon echoes at this 0?C1 transition coincides with the polarization of the second exciting pulse for all combinations of linear and circular polarizations of exciting radiation pulses. Photon echo does not appear either for linear orthogonal or for opposite circular polarizations of exciting pulses in pure ytterbium. In mixtures of ytterbium with atomic buffers (Kr, Xe), collision induced photon echo arises only for exciting pulses of linear orthogonal polarizations, its power is essentially less than that of the ordinary echo generated by pulses with parallel polarizations in the same mixture. Polarization of collision induced echo is linear, and it coincides with polarization of the first exciting pulse. Experimental results agree with calculations, and they confirm that the collision induced photon echo at this transition arises exclusively due to anisotropy of depolarizing collisions.     

Velocity effects in atomic and molecular collisions: Study by coherent transients

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.     

Effect of magnetic field on the stimulated photon echo in ytterbium vapors

Polarization of the stimulated photon echo (SPE) at the 0 ? 1 transition in ytterbium vapors in the presence of a longitudinal magnetic field of 0–40 G is experimentally and theoretically studied. The SPE is generated using three light pulses with identical linear polarizations, so that the SPE polarization is the same at zero magnetic field. In the presence of a weak magnetic field, the SPE polarization vector rotates around the magnetic field vector and the depolarization of the SPE signal takes place. Each of the SPE polarization components exhibits biharmonic oscillations depending on the magnetic field. In the presence of a strong magnetic field, these oscillations vanish and the SPE becomes depolarized. The experimental data are in qualitative agreement with the results of the numerical calculations performed with the method of the evolution operator for the finite-duration excitation pulses. The application of the results for the processing of optical data is discussed.     

Photon echo and stimulated photon echo study of various collisional-relaxation channels

Collisional relaxation in SF₆ gas and its mixtures with He and Xe is studied by photon echo and stimulated photon echo methods from the standpoint of the possibility of identifying the contributions of different types of collisions. The nonexponential nature of the kinetic curve of the photon echo is clearly observed for pure SF₆, it is weaker in the mixture SF₆+Xe, and it is virtually completely absent for high degrees of dilution of SF₆ with helium. These features can be explained on the basis of estimates, made from experimental data, of the critical delay between the exciting pulses (for which the nonexponential behavior should be most strongly manifested). In pure SF₆ it is possible to distinguish the contribution of the inelastic channel (rotational relaxation) and the contribution of weak collisions. To distinguish successfully the relaxation channels in mixtures with buffer gases a heavier buffer gas and a much better time resolution must be used. It is shown that data obtained on the orientation and alignment relaxation rates by the stimulated photon echo method can serve as an upper limit for the rates of inelastic processes which cannot be measured by the photon echo method. The combined use of photon echo and stimulated photon echo methods made it possible to obtain data on the cross sections for elastic and inelastic scattering of the collisional pairs SF₆–SF₆, SF₆–Xe, and SF₆–He. Zh. éksp. Teor. Fiz. 116, 47–56 (July 1999)     

Depolarizing collisions in ytterbium vapor: Isotropic and anisotropic relaxation

Isotropic depolarizing collisions are studied using a stimulated photon echo with a specific polarization of the excitation radiation pulses in a mixture of ytterbium with krypton for the J = 1 ? J = 0 transition of ¹⁷⁴Yb. The difference between the relaxation rates of orientation and alignment γ _b ⁽²⁾ ? γ _b ⁽¹⁾ of the ³ P ₁(6s6p) ¹⁷⁴Yb level is measured as a function of the krypton pressure. The collision photon echo at the J = 1 ? J = 0 transition induced by the anisotropic relaxation is studied for the Yb + Xe mixture. The power of the collision echo increases from zero with the addition of a buffer gas to ytterbium, reaches an optimal level, and decreases with an increase in the buffer gas pressure. The polarization of this collision-induced echo differs from the polarization of the conventional echo. The experimental results are in qualitative agreement with theoretical predictions.     

UV-induced generation of rare tautomers of 2-thiouracils: a matrix isolation study

Unimolecular photoisomerization reactions were studied for 2-thiouracil, 6-aza-2-thiothymine, 1-methyl-2-thiouracil, and 3-methyl-2-thiouracil isolated in low-temperature Ar matrixes. The IR spectra have revealed that before UV irradiation all the matrix-isolated compounds adopted exclusively the oxo-thione tautomeric form. Upon UV (lambda > 320 nm) irradiation of the matrixes, two oxo-thiol photoproducts were generated for monomeric 2-thiouracil as well as for monomeric 6-aza-2-thiothymine. Generation of these products corresponds to transfer of a proton from either the N(1)-H or N(3)-H group to the sulfur atom of the C(2)=S thiocarbonyl moiety. The first of the above reactions was photoreversible. As a consequence, after prolonged UV irradiation most of the material was transformed into the oxo-thiol-N(1)H form. The hydroxy-thiol tautomers of 2-thiouracil and 6-aza-2-thiothymine were also photogenerated as minor products. For 1-methyl-2-thiouracil and 3-methyl-2-thiouracil, thione --> thiol phototautomeric reactions yielded the oxo-thiol isomers of the compounds. Since these reactions were photoreversible, the final stages of the photoinduced processes corresponded, for both methylated 2-thiouracils, to photostationary states. All the products of the investigated photoreactions were identified by comparison of their IR spectra with the spectra calculated at the DFT(B3LYP)/6-311++G(2d,p) level.