Franck-Condon factors and relative strengths of the c1Σu → α1Δg,c1Σu → X3Σg electronic transitions in the O2 molecule

Translated from Zhurnal Prikladnoi Spektroskopii, Vol. 54, No. 1, pp. 46–50, January, 1991.     

The frequency scale of speech intonation.

In intonation research, prominence-lending pitch movements have either been described on a linear or on a logarithmic frequency scale. An experiment has been carried out to check whether pitch movements in speech intonation are perceived on one of these two scales or on a psychoacoustic scale representing the frequency selectivity of the auditory system. This last scale is intermediary between the other two scales. Subjects matched the excursion size of prominence-lending pitch movements in utterances resynthesized in different pitch registers. Their task was to adjust the excursion size in a comparison stimulus in such a way that it lent equal prominence to the corresponding syllable in a fixed test stimulus. The comparison stimulus and the test stimulus had pitches running parallel on either the logarithmic frequency scale, the psychoacoustic scale, or the linear frequency scale. In one-half of the experimental sessions, the test stimulus was presented in the low register, while the comparison stimulus was presented in the high register, and, conversely, for the other half of the sessions. The result is that, in all cases, stimuli are matched in such a way that the average excursion sizes in different registers are equal on the psychoacoustic scale.     

Fast and efficient preparation of Baylis-Hillman-derived (E)-allylic azides and related compounds in aqueous medium

A practical access to alkyl- and aryl-substituted (E)-2-(azidomethyl)alkenoates and related azido compounds from the corresponding allylic bromides in aqueous acetone is described. An alternative method to obtain the starting bromides based on heterogeneous catalysis under mild conditions was also investigated.     

Molecular dynamics simulation of processing using AFM pin tool

A three-dimensional molecular dynamics (MD) model is utilized to investigate the effect of tool geometry on the deformation process of the workpiece and the nature of deformation process at the atomic-scale. Results show that different states exist between the atomic force microscope (AFM) pin tool and the workpiece surface, i.e. the non-wear state, the ploughing state, the state in which ploughing is dominant and the state in which cutting plays a key role. A relationship between the deformation process of the workpiece and the potential energy variation is presented. The potential energy variation of atoms in different deformed regions in the workpiece such as plastically deformed region, elastically deformed region and the mixed deformation region is different. The features of variations of potential energy are discussed.     

Enantiodiscrimination of racemic electrophiles by diketopiperazine enolates: asymmetric synthesis of methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates

Enolates of (S)-N,N′-bis-(p-methoxybenzyl)-3-iso-propylpiperazine-2,5-dione exhibit high levels of enantiodiscrimination in alkylations with (RS)-1-aryl-1-bromoethanes and (RS)-2-bromoesters, affording substituted diketopiperazines containing two new stereogenic centres in high de. Deprotection and hydrolysis of the resultant substituted diketopiperazines provides a route to the asymmetric synthesis of homochiral methyl 2-amino-3-aryl-butanoates and 3-methyl-aspartates in high de and ee.     

Irregularities of distribution with respect to strips

Summary A lower bound is established for the strip discrepancy of a broad class of point distributions. The bound implies unbounded strip discrepancy for equally weighted point distributions under favorable conditions. The methods of proof use notions from integral geometry.     

EPR-detected photoinduced electron transfer in three structurally related molecular triads

A comparative electron paramagnetic resonance (EPR) study has been performed on a series of structurally related molecular triads which undergo photoinduced electron transfer and differ one from the other in terms of the acceptor or donor moieties. The molecular triads, C-P-C₆₀, TTF-P-C₆₀ and C-P-P_F, share the same free-base, tetraarylporphyrin (P) as the primary electron donor, which after light excitation initiates the electron transfer process, but differ either in terms of the electron acceptor (fullerene derivative, C₆₀, versus fluorinated free-base porphyrin, P_F), or in terms of the final electron donor (carotenoid polyene, C, versus tetrathiafulvalene, TTF). All these molecular triads can be considered artificial photosynthetic reaction centers in their ability to mimic several key properties of the reaction center primary photochemistry. Photoinduced charge separation and recombination have been followed by time-resolved EPR in a glass of 2-methyltetrahydrofuran and in the nematic phase of the uniaxial liquid crystal E-7. All the triads undergo photoinduced electron transfer, with the generation of charge-separated states in both the low-dielectric environment of the 2-methyl-tetrahydrofuran glass and in anisotropic E-7 medium. Different photochemical pathways have been recognized depending on the specific donor and acceptor moieties constituting the molecular triads. In the presence of the tetrathiafulvalene electron donor singlet- and triplet-initiated electron transfer routes are concurrently active. Recombination to the low-lying carotenoid triplet state occurs in the carotene-based triads, while singlet recombination is the only active route for the TTF-P-C₆₀ triad, where a low-lying triplet state is lacking. Long-lived charge separation has been observed in the case of TTF-P-C₆₀: about 8 μs for the singlet-born radical pair in the glassy isotropic matrix and about 7 μs for the triplet-born radical pair in the nematic phase of E-7. For all the molecular triads, a weak exchange interaction (J?1 G) between the electrons in the final spin-correlated radical pair has been evaluated by simulation of the EPR spectra, providing evidence for superexchange electronic interactions mediated by the tetraarylporphyrin bridge.     

Structural and electronic properties of graphite layers grown on SiC(0 0 0 1)

Photoelectron spectroscopy, low-energy electron diffraction, and scanning probe microscopy were used to investigate the electronic and structural properties of graphite layers grown by solid state graphitization of SiC(0 0 0 1) surfaces. The process leads to well-ordered graphite layers which are rotated against the substrate lattice by 30°. On on-axis 6H-SiC(0 0 0 1) substrates we observe graphitic layers with up to several 100 nm wide terraces. ARUPS spectra of the graphite layers grown on on-axis 6H-SiC(0 0 0 1) surfaces are indicative of a well-developed band structure. For the graphite/n-type 6H-SiC(0 0 0 1) layer system we observe a Schottky barrier height of ?_B,n = 0.3 ± 0.1 eV. ARUPS spectra of graphite layers grown on 8° off-axis oriented 4H-SiC(0 0 0 1) show unique replicas which are explained by a carpet-like growth mode combined with a step bunching of the substrate.     

Schrödinger Uncertainty Relations and Physical Features of Correlated-Coherent States

We show that the difference between the Schrödinger uncertainty relations (UR) and the Heisenberg UR is fundamental. We propose a modified version of stochastic mechanics that allows clearly demonstrating that the contributions from the anticommutator and the commutator to the Schrödinger UR are equally important. A classification of quantum states minimizing the Schrödinger UR at an arbitrary instant is proposed. We show that the correlation of the coordinate and momentum fluctuations in such correlated-coherent states (CCS) is largely determined by the contributions from not only the commutator but also the anticommutator of the corresponding operators. We demonstrate that the character of this correlation changes qualitatively in time from the antiphase correlation typical for the Heisenberg UR to the inphase correlation for which the contribution from the anticommutator is decisive. We comparatively analyze properties of a free microparticle and a quantum oscillator in CCS and show that the CCS correspond to traveling-standing de Broglie waves in both models.