Laser probes of intramolecular energy transfer between internal rotation and vibrations in large polyatomics

Laser excited S₁→S₀ fluorescence spectra are obtained from p-fluorotoluene in a supersonic jet in order to probe internal rotational-vibrational coupling. Resolved fluorescence spectra after selective excitation of S₁ levels with high quanta states of the CH₃ internal rotation contain evidence of extensive interactions with isoenergetic vibrational levels. Analogous spectra from states without excitation of the internal rotor show little or no interactions. The results are consistent with a recently developed theory of the intramolecular collisional transfer of rotor energy to the vibrational field.     

S1-S0 fluorescence after narrow band excitation of glyoxal: Single rotational level fluorescence and a technique for deconvolution of Doppler congested absorptions

Individual rovibronic transitions are isolated at high resolution from a crowded absorption feature with a fluorescence excitation technique which is based on detection of fluorescence from one and only one rovibronic level. The method is illustrated by resolving four rovibronic transitions from the single rotational line-like feature in the 0, 0 band of the ${}^1\text{A}{}_{\mathrm{u}}\text{←}{}^1\text{A}{}_{\mathrm{g}}$ (S₁ ← S₀) absorption of glyoxal vapor. The rotational structure of the 5₁⁰ fluorescence band is studied as a function of tuning a narrow-band laser line (linewidth < 10^?4 cm^?1) to various positions in and near this absorption feature. The fluorescence structure proves an extremely sensitive tool for detecting small absorptions, with emission from 12 rovibronic levels being identified. One of the spectra so obtained is a close approximation of true single rotational level fluorescence.     

Tunable Pentapeptide Self‐Assembled β‐Sheet Hydrogels

Oligopeptide‐based supramolecular hydrogels hold promise in a range of applications. The gelation of these systems is hard to control, with minor alterations in the peptide sequence significantly influencing the self‐assembly process. We explored three pentapeptide sequences with different charge distributions and discovered that they formed robust, pH‐responsive hydrogels. By altering the concentration and charge distribution of the peptide sequence, the stiffness of the hydrogels could be tuned across two orders of magnitude (2–200 kPa). Also, through reassembly of the β‐sheet interactions the hydrogels could self‐heal and they demonstrated shear‐thin behavior. Using spectroscopic and cryo‐imaging techniques, we investigated the relationship between peptide sequence and molecular structure, and how these influence the mechanical properties of the hydrogel. These pentapeptide hydrogels with tunable morphology and mechanical properties have promise in tissue engineering, injectable delivery vectors, and 3D printing applications.     

Collision induced intersystem crossing the photophysics of glyoxal vapor excited at 4358 Å

The yields, lifetimes and spectra of singlet ¹A_u (S₁) and triplet ³A_u (T₁) emissions from glyoxal vapor (0.003 to 10 torr) have been measured after initially pumping levels about 1000 cm^?1 above the S₁ zero-point level with the 4358 A Hg line and with flash excitation centered at 4345 A. Only S₁ emission is observed at the lowest pressures. The singlet fluorescence contains appreciable structure from the zero-point level even when the hard sphere collision interval exceeds the radiative lifetime calculated from the absorption coefficient. Implications of long lifetimes (due to S₁ - T₁ vibronic interactions) are not confirmed by pulsed excitation studies. Both S₁ and T₁ emissions are observed at pressures above about 0.1 tert and both are self-quenched. However, added gases such as cyclohexane, argon, and helium selectively quench only S₁ emission. This quenching is collision-induced S₁→T₁ intersystem crossing with cross sections of order 0.1 hard sphere for transitions from the S₁ zero-point level. The triplet yield in 0.2 torr of pure glyoxal is probably near unity, and the subsequent crossing T₁ → S₀, if it occurs, lies in the statistical limit. Indications of fast nonradiative decay from high triplet vibrational levels are seen in the phosphorescence yields. Self-quenching of the triplet state appears to be associated with the photochemical activity of glyoxal.     

The triple-twist map: Generator of a four-dimensional uniform stochastic web

The system consisting of three identical harmonic oscillators impulsively coupled can be described by the four-dimensional triple-twist map. This map is capable of generating a uniform stochastic web, periodic in all four dimensions. Some properties of this web are studied.     

Deterministic chaos in a quantum mechanical system described by a time-independent Hamiltonian: A model of three Josephson junctions in a loop

Quantum mechanical equations of motion are obtained for a system consisting of a very large number of three types of interacting bosons. Under suitable choice of parameters of the Hamiltonian of the system, the equations of motion are those describing three Josephson junctions in a superconducting loop. It is shown numerically that this system is capable of exhibiting deterministic chaos (extreme sensitivity to initial conditions).     

On intensity perturbations in vibronically induced radiative transitions

Intensity perturbations in forbidden radiative transitions due to cubic anharmonic mixing involving the inducing mode and a totally symmetric progression-forming mode are discussed. It is shown that such mixing will lead to deviations from mirror symmetry of the absorption and fluorescence structure because the destructive-constructive interference pattern which prevails in absorption is different to that in emission. This analysis is applied to intensities in the 2600 Å system of benzene. Moderate cubic coupling energies (ca. 10 cm^-1) have marked effects on intensity distributions even when the interacting levels are 200 cm^-1 apart. The splitting of the progressions 1₀ ⁿ 6₁ ² and 1 _n ⁰6₂ ¹ into two sub-progressions (l=0, 2) is linearly dependent on the extent of vibronic excitation in the a _1g mode v ₁. These effects are amenable to experimental detection.