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.     

Christoffel-Darboux-type formulae and a recurrence for biorthogonal polynomials

It is proved that biorthogonal polynomials obey two different kinds of Christoffel-Darboux-type formulae, one linking polynomials with a different parameter and one combining polynomials with different degrees. This is used to produce a mixed recurrence relation, which is valid for all biorthogonal polynomials. This recurrence relation establishes several results on interlacing property of zeros of successive biorthogonal polynomials and leads to a new result on the interlace of zeros of orthogonal polynomials (of equal degrees) with respect to two distributionsdψ(x) andx ^p dψ(x), 0<p≤1, with support in either [0, 1] or [1, ∞).     

Three Electrons in a Two-Dimensional Parabolic Trap: The Relative Motion Solution

In agreement with the Kohn theorem the relative motion (rel) of three electrons in a two-dimensional parabolic trap separates from the centre-of-mass (CM) motion. By introducing new coordinates the Hamiltonian for relative motion in the approximation of non-interacting electrons can be taken to the normal form. The eigenstates of the normalized Hamiltonian are products of the Fock-Darwin states for normal modes. The energy levels for relative motion are obtained by diagonalizing the exact Hamiltonian in the eigenbasis for the non-interacting case. In this basis the interaction matrix elements can be obtained in the analytical form. Since the rank of the Hamiltonian matrix is significantly reduced, the calculations are faster and more accurate than those for the full (CM + rel) motion. This advantage is especially important for the calculations of excited states and the analysis of energy spectra.     

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.     

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.     

On Periodic Solutions of Degenerate Singularly Perturbed Linear Systems with Multiple Elementary Divisor

We establish sufficient conditions for the existence and uniqueness of a periodic solution of a system of linear differential equations with a small parameter and a degenerate matrix of coefficients of derivatives in the case of a multiple spectrum of a boundary matrix pencil. We construct asymptotics of this solution.