Collisional deexcitation of exotic hydrogen atoms in highly excited states

The deexcitation of exotic hydrogen atoms in highly excited states in collisions with hydrogen molecules has been studied using the classical-trajectory Monte Carlo method. The Coulomb transitions with large change of principal quantum number n have been found to be the dominant collisional deexcitation mechanism at high n. The molecular structure of the hydrogen target is shown to be essential for the dominance of transitions with large Δn. The external Auger effect has been studied in the eikonal approximation. The resulting partial wave cross-sections are consistent with unitarity and provide a more reliable input for cascade calculations than the previously used Born approximation. Received 28 May 2002 Published online 15 October 2002 RID="a" ID="a"e-mail: thomas@physik.unizh.ch     

Collisional deexcitation of exotic hydrogen atoms in highly excited states

The atomic cascades in μ^- p and p atoms have been studied in detail using new results for the cross-sections of the scattering of highly excited exotic atoms from molecular hydrogen. The cascade calculations have been done with an updated version of the extended standard cascade model that computes the evolution in the kinetic energy from the beginning of the cascade. The resulting X-ray yields, kinetic energy distributions, and cascade times are compared with the experimental data.     

Reactions of excited atoms and molecules with atoms and molecules

Penning electron distributions arising from the ionization of Na and K by He (1s 2s ^1,3 S)-metastables in thermal collisions, as well as the absolute cross section for Penning ionization of Na by He (2³ S) and relative cross sections for ionization of Na and K by He(2¹ S) and He(2³ S) are measured. It is shown that under fairly general conditions the well depth ε* of the interaction potential between the metastable and the target particle can be obtained directly from the measured electron distributions. ε*-values are reported for the moleules He(1s 2s ^1,3 S)-Na(² S), K(² S) (^2,2Ω), and for He(1s 2s ^1,3 S)-Hg(¹ S)(^1,3Ω). These latter values are obtained from previously published measurements and are to be considered preliminary. Further, additional evidence is given, that Penning ionization with metastables is an electron exchange process.     

Reactions of excited atoms and molecules with atoms and molecules

From a He-beam excited by electron impact we eliminated the He(2¹ S) component to better than 0.5% by irradiating light from a He discharge. The quenching process ishv(2¹ P→2¹ S)+He(2¹ S)→He(2¹ P)→He(1¹ S +hv) (2¹ P 1)¹ S. By measuring the ions produced in collisions of the He-metastables with various target gases in a mass spectrometer, singlet to triplet Penning-cross section ratios were obtained. These ratios are without exception close to one, which is taken as evidence for the previously proposed electron exchange mechanism of the Penning ionization. In the case that more ions are produced in the collision of He (2¹ S) and He(2³ S) with a target gas, separate relative production cross sections are obtained for the two metastables. For the rare gases the measurements are performed at two temperatures of the He-beam, 320 and 90 °K. It is found that the cross section ratio of associative — to Penning ionization increases considerably as the temperature is decreased for both, He(2¹ S) and He(2³ S), the effect being much more pronounced for He(2¹ S). The results of this work are found to confirm conclusions drawn from measured energy distributions of the electrons ejected in the Penning process.     

Reactions of excited atoms and molecules with atoms and molecules

Ionizing collisions of long lived excited particles with atoms and molecules are studied by a cross beam technique. For the first time reactions of atoms in high Rydberg states are included in the investigation. In this paper we report relative cross sections for the production of the ions RH⁺, RH ₂ ⁺ , and H ₂ ⁺ by collisions of excited rare gas atoms R^* with H₂. With HD as the target molecule the isotope effect for the production of RD⁺ and RH⁺ has been determined. In the case of argon and krypton, ions are produced only by the high Rydberg states, whereas in the case of helium and neon only the metastable states contribute to a measurable extent. The data indicate, that the reaction mechanism is different in principle for metastable and highly excited atoms. Simple models are proposed to explain the experimental results.     

Ionization of long-lived highly excited atoms by collision with molecules. II

A theoretical treatment of the collisional ionization of a highly excited atom with a molecule is improved by use of the exact form factor of the hydrogen atom in highly excited states. The present treatment is still based on the previously proposed mechanism in which the Rydberg electron is ionized by gain of energy from rotational de-excitation of the molecule in a rotationally excited state. Closer comparison of experiment with theory is made for symmetric- as well as asymmetric-top molecules.     

Emission of highly excited atoms and molecules in the upper atmosphere

The emission ability of Rydberg atoms and molecules in the orbitally degenerate states is considered. The mechanisms of their formation in the F, E, and D upper atmosphere layers are analyzed. The characteristic lifetimes of these states in the microwave range are estimated. It is shown that radiation in this range can be accompanied by a cascade of transitions. The possibility of studying the influence of intense atmospheric microwave radiation on living organisms is discussed.     

Method of describing highly excited vibrational-rotational states of diatomic molecules

Institute of Applied Physics, Academy of Sciences of the USSR. Translated from Izvestiya Vysshikh Uchebnykh Zavedenii, Radiofizika, Vol. 33, No. 3, pp. 281–289, March, 1990.     

Bimolecular gas-phase processes with the participation of vibrationally excited triplet molecules of aromatic ketones

Time-resolved moderated luminescence of aromatic ketones (benzophenone, aceptophenone) in the presence of neutral and reactive hydrogeneous foreign gases (ethylene, pentane, triethylamine) is investigated. It is shown that the addition of hydrogeneous foreign gases leads to strong quenching of the triplet molecules of aromatic ketones. Effectivenesses of such bimolecular processes as the collision detachment of a hydrogen atom and establishment of vibrational and thermal equilibrium are compared. It is concluded that the vibrational degrees of freedom of the acceptors, the aromatic ketones, are inactive in the photochemical process of collision detachment of a hydrogen atom that takes place after the establishment of vibrational equilibrium. Institute of Molecular and Atomic Physics of the National Academy of Sciences of Belarus, 70, F. Skorina Ave., Minsk, 220072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 1, pp. 73–77, January–February, 1999.     

Collisional deactivation of vibrationally excited triplet molecules of fluorenone

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 55, No. 4, pp. 607–612, October, 1991.     

How to get access to long range states of highly excited molecules

Due to competition between ionic and covalent dissociation, the excited potential curves of the alkali dimers display long range structures, leading in some cases to secondary wells. We discuss the possibility of populating the well (with a depth of 1614.8 cm^-1, located at R _e = 30.5a ₀ ) that is present in the Na₂ potential curve and propose detection schemes. Received: 28 May 1998 / Revised: 5 August 1998 / Accepted: 24 September 1998     

Tunable Wigner states with dipolar atoms and molecules

We study the few-body physics of trapped atoms or molecules with electric or magnetic dipole moments aligned by an external field. Using exact numerical diagonalization appropriate for the strongly correlated regime, as well as a classical analysis, we show how Wigner localization emerges with increasing coupling strength. The Wigner states exhibit nontrivial geometries due to the anisotropy of the interaction. This leads to transitions between different Wigner states as the tilt angle of the dipoles with the confining plane is changed. Intriguingly, while the individual Wigner states are well described by a classical analysis, the transitions between different Wigner states are strongly affected by quantum statistics. This can be understood by considering the interplay between quantum-mechanical and spatial symmetry properties. Finally, we demonstrate that our results are relevant to experimentally realistic systems.     

Influence of the medium on the electromagnetic radiation spectrum of highly excited atoms and molecules

The influence of neutral species in the E- and D-layers of the Earth’s upper atmosphere on the spectrum of the spontaneous emission (absorption) of Rydberg atoms and molecules for transitions that occur without changing the principal quantum number (Δn = 0) is examined. Along with the process of l-mixing, the splitting of orbitally degenerate states due to interaction with perturbing neutral species of the medium is taken into account. The possible types of radiative transitions between them are analyzed. It is demonstrated that, for principal quantum numbers of n = 10–30, decimeter-band radiation corresponds to transitions between the levels of split states, whereas meter-band radiation, to transitions between their individual components. It is established that, for these values of n, the ratios of the intensities of the decimeter and meter bands for Δn = 0 transitions to the intensity of IR radiation (Δn = 1) are 10⁻⁴ and 10⁻⁶, respectively. The issue of satellite signal phase shift because of multiple Raman scattering in the D-layer of the atmosphere is discussed.     

Relaxation processes with participation of excited S 1 and T 1 states of spatially distorted meso-phenyl-substituted octamethylporphyrins

We have performed comparative analysis of the spectral properties and photophysical parameters of spatially distorted octamethylporphyrins (OMPs) upon varying the number (from one to four) and position of bulky meso-phenyl substituents in liquid solutions at 293 K and in solid media at 77 K. It has been substantiated that, for the series of studied compounds, which are characterized by a high degree of nonplanar distortions, considerable changes in the spectral-kinetic properties of singlet and triplet states at 293 K in liquid solutions are determined by the dynamic relaxation of the tetrapyrrole macrocycle that is caused by steric interactions of meso-phenyls with neighboring bulky groups ??-CH₃. The decay of T ₁ states of mono- and di-meso-phenyl-substituted (trans) OMP molecules in liquid solutions has a biexponential character, which is indicative of conformational rearrangements of the macrocycle in the T ₁ state. We are the first to measure the phosphorescence of spatially distorted metal-free OMP molecules in solid solutions at 77 K. It has been sub-stantiated that the decrease in the phosphorescence lifetime and quantum yield observed in the series of studied compounds with increasing number of meso-phenyl substituents at 77 K is related to a gradual increase in the probability of the nonradiative intersystem crossing, caused by the lowering of the energy of the T ₁ level. We have revealed that spatially distorted tetrapyrrole macrocycles in rigid media at 77 K in the ground state are represented by two conformations. It has been found that the oxygen quenching rate constants of excited S ₁ and T ₁ electronic states of planar and spatially distorted porphyrin molecules are close to each other and depend weakly on the character distortion of the macrocycle. We have shown that the singlet oxygen generation quantum yield (??_??) of studied compounds depends on the number of meso-phenyl substituents in the OMP molecule and is determined by the character of the conformational dynamics of the tetrapyrrole macrocycle at 293 K.     

Calculations of the excited states of atoms

The possibility of calculating the approximate wave functions of the excited states of a many-electron atom by means of extremalization of the variation functional is discussed. The calculation of helium 1s2s ¹ S and X-ray K-state of neon was carried out in this way assuming the wave functions expressed in the analytical form. The results obtained are satisfactory compared with those obtained by other methods as well as compared with experiment.The author would like to thank Dr. E. Antoník for many discussions on the problems of this paper and the management of the Institute of Technical Physics for its all-round support. He also thanks his wife and Mrs. K. Trnková for carefully carrying out the tedious calculations.     

From coherently excited highly correlated states to incoherent relaxation processes in semiconductors

Recent theories of highly excited semiconductors are based on two formalisms, referring to complementary experimental conditions, the real-time nonequilibrium Green's function techniques and the coherently controlled truncation of the many-particle problem. We present a novel many-particle theory containing both of these methods as limiting cases. As a first example of its application, we investigate four-particle correlations in a strong magnetic field including dephasing resulting from the growth of incoherent one-particle distribution functions. Our results are the first rigorous solution concerning formation and decay of four-particle correlations in semiconductors. They are in excellent agreement with experimental data.     

A resonance-reman-scattering multifrequency spectrometer for investigating excited states of molecules and photoinduced high-rate processes

A resonance-Raman-scattering multifrequency laser spectrometer operating in a wide spectral range (355–750 nm) and making possible the recording of both stationary Raman spectra and spectra with a time resolution of up to 100 psec in the time interval of 0–50 nsec has been developed. The spectrometer has been used with advantage for the study of the excited states of molecules of metalloporphyrins in solutions and processes of interaction of model metalloporphyrins with DNA and DNA-modeling polynucleotides. To whom correspondence should be addressed. B. I. Stepanov Institute of Physics, National Academy of Sciences of Belarus 68, F. Skorina Ave., Minsk, 210072, Belarus. Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 66, No. 5, pp. 726–733, September–October, 1999.