Spectro-streak picosecond studies of intramolecular charge-transfer fluorescence

A spectro-streak photometer, an instrument for simultaneously measuring fluorescence intensity, time, and wavelength,I(t, ), with a single picosecond excitation pulse, has been constructed. Two typical and currently highly topical examples of mesurements are discussed. (1) the temporal development of the fluorescence form the intramolecular charge-transfer (ICT) state of the rigid aromatic compound 4,5-(1-methylindolino)3,4-naphthanthracene is studied in the protic solvent hexanol. (2) Propyl chain-linked pyrene/N,N-dimethylaniline is used as the model compound to study conformational changes associated with the transition from a contact ion pair to a sandwich exciplex.     

Method of polarization reflection matrix measurement in the submillimeter wave range

Homodyne method of measurement of polarization reflection matrix, providing the possibility of simultaneous measurement of all four complex coefficients of polarization reflection matrix in submillimeter quasi-optical (QO) circuits is presented. Technical realizability of the method for QO waveguides of the class of "hollow dielectric wavequide" is shown.     

Investigation of superconductivity effects in single-phase and multiphase Bi2Sr2CaCu2O8 single-crystals at 2-MM wavelengths

Experimental investigations of superconductivity effects in single-phase and multiphase Bi₂Sr₂CaCu₂O₈ single-crystals have been carried out at 142 GHz frequency by means of the standing wave profile method [1]. Josephson harmonic generation has been observed to be responsible for the appearence of additional peaks on the standing wave profile of the open dielectric resonator loaded with a properly orientated multiphase high-T_c superconductor specimen. This leads to the conclusion that most of the Josephson junctions in multiphase crystals are located in certain crystallographic planes. The investigations of temperature dependencies showed that sharp resonant peaks of conductivity observed earlier [2] at 60 GHz could also be observed at 142 GHz.     

Travelling, non-periodic patterns in nonlinear stability problems

In this short note we present results on the existence of several classes of travelling, non-periodic solutions of the complex Ginzburg-Landau equation. First we give a very short introduction to the G-L equation and show its importance in nonlinear stability theory. We then study the G-L equation with complex coefficients and establish the existence of a 2-parameter family of quasi-periodic solutions and two different types of one-parameter families of heteroclinic orbits; all members of these families travel with a well-defined wave-speed. The heteroclinic solutions correspond to (travelling) soliton-like localized structures which connect different (stable) periodic patterns. Mathematically, these families of travelling solutions (quasi-periodic and heteroclinic) are continuations into the complex case of the stationary solutions of the real G-L equation.     

MULTIPHOTON EXCITATION OF A WATER MOLECULE IN INTENSE LASER FIELDS

A stretch vibration Hamiltonian of H_2O has been derived by using the second quantization, unitary transformations and the optimization of coefficients. The energy spectrum obtained from this Hamiltonian is in good agreement with that of experiments. The multiphoton excitation and the energy absorption of H_2O in intense laser fields have been calculated.     

Design of a new molecule that exhibits observable CD spectra under σ-σ* excitation: 2,6-Disilyl-2,6-disilaspiro[3.3]heptanes

Abstract

We previously designed and prepared the first molecules to exhibit observable CD spectra by n-σ* excitation, 2,6-dithiaspiro[3.3]heptane 2,6-dioxide. Spiro[3.3]heptane frameworks possess axial asymmetry due to puckering of 2 four-membered rings; the ring bonds are rich in p-character due to acute bond angles, which lowers the σ* energy levels. In contrast, the lone pairs are rich in s-character, which results in a good donor with conformational fixation. We expected that, instead of lone pairs as donating orbitals, the use of σ-electron-donating Si-Si bonds should result in UV absorption in the observable range (>180?nm), so that the Cotton effect could appear, at least partially, in that range. We designed 2,6-disilyl-2,6-disilaspiro[3.3]heptanes as models, and performed theoretical calculations to confirm our idea.     

Solitons in Josephson junctions: An overview

The dynamics of the Josephson tunnel junction is approximately described by a perturbed sine-Gordon equation. The Josephson tunnel junction is thus a convenient experimental solid state device for the study of solitons and solitonlike phenomena. The physical manifestation of the soliton is a propagating magnetic flux quantum ( ₀=h/2e=2.064×10^–15 V sec). Basic properties of the soliton and its relation to observable experimental quantities (zero field steps, microwave radiation, etc.) are reviewed. Recent direct measurements of the actual soliton profile are also mentioned.     

Triplet states of humic acids studied by laser flash photolysis using different excitation wavelengths

The spectra and kinetics of short-lived intermediates formed from aqueous (0.1 N NaOH) solutions of the natural mixture of humic and fulvic acids (HFA) were studied by laser flash photolysis using excitation wavelengths of 337, 390, 470, and 520 nm. Laser photolysis of HFA with light of 520 and 470 nm results in the formation of triplet excited states (T_HFA) characterized by the broad absorption spectrum with a maximum near 630 nm and lifetimes of 0.15 ms in deoxygenated solutions. The formation of two types of T_HFA with lifetimes of 0.1 and 2 ms and absorption spectra with maxima at 570 nm is observed under photolysis with light of 337 and 390 nm. The estimation of quantum yields of T_HFA gives 1 and 0.3% under photolysis with excitation wavelengths of 337 and 520 nm, respectively. The rate constants of T_HFA quenching by molecular oxygen are equal to (7—8)·10⁸ L mol^–1 s^–1.     

Polarized basis sets of Slater-type orbitals: H to Ne atoms

We present three Slater-type atomic orbital (STO) valence basis (VB) sets for the first and second row atoms, referred to as the VB1, VB2, and VB3 bases. The smallest VB1 basis has the following structure: [3, 1] for the H and He atoms, [5, 1] for Li and Be, and [5, 3, 1] for the B to Ne series. For the VB2 and VB3 bases, both the number of shells and the number of functions per shell are successively increased by one with respect to VB1. With the exception of the H and Li atoms, the exponents for the VB1 bases were obtained by minimizing the sum of the Hartree-Fock (HF) and frozen-core singles and doubles configuration interaction (CISD FC) energies of the respective atoms in their ground state. For H and Li, we minimized the sum of the HF and CISD FC energies of the corresponding diatoms (i.e., of H(2) or Li(2)) plus the ground-state energy of the atom. In the case of the VB2 basis sets, the sum that was minimized also included the energies of the positive and negative ions, and for the VB3 bases, the energies of a few lowest lying excited states of the atom. To account for the core correlations, the VBx (x = 1, 2, and 3) basis sets for the Li to Ne series were enlarged by one function per shell. The exponents of these extended (core-valence, CV) basis sets, referred to, respectively, as the CVBx (x = 1, 2, and 3) bases, were optimized by relying on the same criteria as in the case of the VBx (x = 1, 2, and 3) bases, except that the full CISD rather than CISD FC energies were employed. We show that these polarized STO basis sets provide good HF and CI energies for the ground and excited states of the atoms considered, as well as for the corresponding ions.     

多光子技术及其应用研究进展

本文综述了多光子技术的基本原理及其在生命科学、化学、物理和材料科学领域的应用研究进展。