Fluorescence polarization of helical molecules cooled in a supersonic jet

The β-binaphthylene oxide molecules studied under supersonic cooling conditions have a number of specific properties due to their nonplanarity. Low-frequency vibrations of the molecules in the excited S1 state are higher than the frequencies for the S0 state, and conversely the high-frequency vibrations have lower frequencies. The S₀-S₂ fluorescence excitation spectrum is structureless. The absence of a Q branch in the rotational contour of the line for the purely electronic transition indicates that it is substantially broadened and shifted toward shorter wavelengths as a result of rotational perturbations of the helical structure of the molecule. Multiplet lines in the spectra of β-binaphthylene oxide complexes with argon, krypton, and xenon correspond to different isomeric complexes. Their bond energies are below those observed previously for planar polycyclic molecules such as perilene, fluorene, and carbazole. The greater number of isomers with xenon is due to strengthening of the bond in the van der Waals complex and the nonequivalence of the position of the xenon atoms on the outside and inside of the helical molecule. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 4, pp. 473–477, July–August, 2006.     

Fine-structure spectroscopy of 2-methylnaphthalene cooled in a supersonic jet

The fluorescence and fluorescence excitation spectra of 2-methylnaphthalene molecules cooled in a supersonic jet are measured. The frequencies of vibrations in the S ₀ and S ₁ states, as well as the relative intensities of electronic-vibrational transitions in the fluorescence and fluorescence excitation spectra, are calculated with the semiempirical MO/M8ST method. The intensities are calculated in the Franck-Condon approximation taking into account the mixing of all the 38 totally symmetric normal vibrations. Based on the calculations, most observed spectral lines are assigned. It is shown that the calculation accuracy of the method is high enough for it to be used to interpret the spectra of molecules of aromatic compounds such as substituted naphthalenes. It is found that the main contribution to the fluorescence spectrum is made by four optically active vibrations.     

The fluorescence excitation spectrum of s-tetrazine cooled in a supersonic free jet

The fluorescence excitation spectrum of the ${}^1\text{B}{}_{\mathrm{3u}}\text{(v′ = 0) ←}{}^1\text{A}{}_{\mathrm{g}}\text{(v″ = 0)}$ transition in s-tetrazine has been observed and measured. The sample was cooled to a rotational temperature of <1 K by expansion in a supersonic free jet. In this way the rotational structure arising from asymmetry split low J lines could be observed. The rotational A and B axes of the ²H₁¹²C₂¹⁴N₄ isotope were observed to interchange upon electronic excitation and a theory describing the effect of this interchange upon the optical selection rules has been developed. Analysis of the resolved rotational structure suggests that the geometry change upon electronic excitation is smaller than that deduced from previous analysis of the room temperature optical spectrum.     

Comparative analysis of high-resolution spectra of naphthalene and its methyl-substituted derivatives cooled in a supersonic jet

We have carried out a comparative analysis of fine-structure fluorescence excitation and fluorescence spectra of naphthalene, 2,6-and 2,7-dimethylnaphthalene, and 2-methylnaphthalene molecules cooled in a supersonic jet. We have shown that both the frequencies and the intensities of most of the lines in the spectra of these molecules are correlated. Such a correlation facilitates interpretation of the spectra in the case when it is difficult to calculate the transition intensities and when lines corresponding to vibrations of different symmetry have close frequencies. For the considered molecules, a preliminary assignment of the lines in the fine-structure spectra is refined. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 74, No. 3, pp. 336–340, May–June, 2007.     

Effect of saturation on vibro-rotational contours in the excitation spectrum of quinizarin cooled in a supersonic jet

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 53, No. 3, pp. 449–456, September, 1990.     

Rotational contours of electronic and electronic-vibrational bands of carbazole complexes with water cooled in a supersonic jet

The rotational contours of the bands corresponding to electronic and electronic-vibrational transitions of the fluorescence excitation spectrum of jet-cooled carbazole complexes with one, two, and three water molecules have been studied. For the carbazole-(H₂O)₁ complex, two bands with a spectral shift of 0.57 cm^?1 were recorded under exposure to radiation with a spectral width of 0.08 cm^?1 at the frequency of the purely electronic transition and some other electronic-vibrational transitions. This is caused by the tunnel effect. The intensities of the shifted low-frequency bands are threefold weaker than those of high-frequency bands due to different values of nuclear spin-statistical weights. In the carbazole-(H₂O)₂ and carbazole-(H₂O)₃ complexes, water molecules are combined into a chain by the hydrogen bond, and the two ends of the chain are hydrogen-bonded to the carbazole molecule. The principal axes I _A and I _B of the moments of inertia in carbazole-(H₂O)₃ have different orientation compared to the other complexes considered, and this leads to an increase in the intensity of the Q-branch.     

Experimental determination and interpretation of the fluorescence and fluorescence excitation spectra of chrysene cooled in a supersonic jet

The fluorescence and fluorescence excitation spectra of jet-cooled chrysene are measured. The frequencies of in-plane vibrations in the ground and first excited singlet electronic states, as well as the relative intensities of transitions between them, are calculated with the MO/M8ST method. Based on these data, experimental spectra are interpreted. In the fluorescence excitation spectrum, the position of the line of the 0–0 transition (28 195 ± 1 cm^?1), which is the most intense, is determined. In the experimental fluorescence excitation spectrum, 21 lines correspond to fundamental vibrations (altogether, 37 lines are attributed). This supports our assignment and is consistent with the group-theoretical analysis of vibronic interactions. Upon excitation at the frequency of the 0–0 transition, 10 lines corresponding to the excitation of fundamental vibrations are detected, and all 17 lines observed are attributed. In the fluorescence excitation spectrum, the standard deviation between the calculated and measured frequencies of attributed fundamental vibrations is 19 cm^?1, while that in the fluorescence spectrum is 15 cm^?1.     

Manifestations of the saturation effect in the polarization of the fluorescence of quinizarin molecules cooled in a supersonic jet

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 53, No. 4, pp. 567–572, October, 1990.     

The characteristics of multiple-photon absorption of SF6 molecules cooled in free jet expansion from a pulsed supersonic nozzle

The multiple-photon absorption of pulsed TEA CO₂ laser radiation by SF₆ molecules cooled toT _R40K andT _v160K in the free jet expansion from a pulsed supersonic nozzle has been investigated at energy fluences of 0.1 to 3.0 J·cm^–2.For practically all laser lines which coincide with the linear absorption spectrum of thev ₃ vibrational mode of SF₆ [P(12)...P(28), 10,6 m], the dependence of the absorbed energyE _ab on the exciting energy fluence was found to be steeper than linearE _abⁿ, wheren=(1.1 to 1.8). Considerable increases of the absorption cross sections with increasing energy fluence were observed.The fraction of the molecules interacting with the laser radiation is estimated.     

The connection between sound production and jet structure of the supersonic impinging jet

An experimental investigation into the sound-producing characteristics of moderately and highly underexpanded supersonic impinging jets exhausting from a round convergent nozzle is presented. The production of large plate tones by impingement on a square plate with a side dimension equal to 12 nozzle exit diameters is studied using random and phase-locked shadowgraph photography. Discrete frequency sound is produced in the near-wall region of the jet when a Mach disk occurs upstream of the standoff shock wave. Tones cease when the plate distance is approximately 2.2 free-jet cell lengths and the first and second shock waves are located in the free-jet positions. The production of impulsive sound appears to be associated with the collapse of the standoff shock wave during a portion of the oscillation cycle. Results from unsteady plate-pressure measurements indicate that plane-wave motion occurs in the impingement region and a secondary pressure maximum is observed on the plate adjacent to the flow region where sound appears to originate.     

Experimental determination and interpretation of fluorescence and fluorescence excitation spectra of 1,2-benzanthracene cooled in supersonic jet

We measured the fluorescence and fluorescence excitation spectra of supersonic jet-cooled 1,2-benzanthracene. Using the MO/M8ST method, we calculated the frequencies of in-plane vibrations in the ground and first excited singlet electronic states, and, in the Franck-Condon approximation, we calculated the intensities of transitions between them. Experimental spectra are interpreted based on these data. In the fluorescence excitation spectrum, the position of the line of the 0–0 transition (26535 ± 1 cm⁻¹), which is the most intense, is determined.     

Spectral characteristics of heterocyclic compounds with a chain structure, cooled in an ultrasonic jet

We have recorded the fluorescence excitation spectra of three heterocyclic compounds with a chain structure [BPO (2-phenyl-5-(4-diphenylyl)oxazole), POPOP (1,4-di[2-(5-phenyloxazolyl)]benzene, and TOPOT (1,4-di[2-(5-n-tolyloxazolyl)]benzene] and the fluorescence spectra of POPOP, under conditions where the molecules were cooled in an ultrasonic helium jet. A line structure is observed in the spectra of POPOP and TOPOT; for the BPO molecules, whose configuration changes considerably during electronic excitation, vibrational structure is apparent only in the low-frequency region of the excitation spectrum, and a diffuse spectrum is recorded starting from ν ₀ ⁰ + 200 cm⁻¹. For all the compounds, in the spectra we recorded vibrations with frequencies up to 100 cm⁻¹, arising due to the flexibility of the molecular structure. The rotational contours of the lines for the electronic and vibronic transitions of the POPOP molecules (T_rot = 10.5 K) and TOPOT molecules (T_rot = 15 K) are structureless and bell-shaped. The degree of polarization of the fluorescence P_fl for the jet-cooled POPOP molecules for excitation of vibrations along the absorption band up to 2000 cm⁻¹ above ν ₀ ⁰ is practically constant (∼8.4%) and matches P_fl for high-temperature vapors. __________ Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 73, No. 6, pp. 728–734, November–December, 2006.     

Flow characteristics of the large scale wave-like structure of a supersonic round jet

A model is developed for the large scale coherent structure of subsonic and supersonic axisymmetric jets. A fluctuation in the jet flow is regarded as being separable into a time-averaged component, a periodic wave-like component and a random small scale component. The small scale fluctuation is viewed as both the driving and dissipative mechanism for the wave-like component. An energy balance model is developed which examines thinterchange of energy between the mean flow and the large scale motion. The effect of wave-like fluctuation amplitude on its own and the mean flow development is examined. Calculations of contours of equal pressure level in the jet near field are made. A model for the mechanism by which locally subsonic components of the wave-like structure may radiate noise to the far field is examined. The method for calculating the radiated noise is discussed.     

Fluorescent spectroscopy of 3-aminophthalimide molecules cooled in an ultrasonic jet

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 50, No. 3, pp. 385–391, March, 1989.     

Isotope-selective infrared multiphoton dissociation of CF3Br in a supersonic free jet

The carbon-isotope selectivity in the multiphoton dissociation of CF₃Br is studied in the collisional region of supersonic free jet. The isotopic abundance of¹²C and¹³C in C₂F₆ formed by recombination of the dissociation products is measured with a quadrupole mass spectrometer. An enrichmet factor of 9.4 is obtained for¹²C with the 9R(30)CO₂ laser line while the factor of 6.9 is obtained for¹³C with the 9P(16) line.     

低温高背压氘团簇源特性研究

为了产生大尺度氘团簇用于与强激光相互作用研究，研制了低温高背压团簇源.利用瑞利散射法对团簇尺度与气体背压相关性和团簇的形成演变过程进行了研究.得到团簇尺度N_c随背压的指数变化关系为N_c∝P^2.89₀，当气体温度为80K，背压P₀为48×10⁵Pa时，氘团簇尺度N_c≈2630，并得到了团 关键词： 氘团簇 团簇源 瑞利散射 激光与团簇相互作用