Formal collision theory indicates that the absolute termolecular recombination reaction rate can be expressed in a form associated either with direct or indirect mechanisms for the recombination. Moreover, the same exact rate constant can be calculated using either of the four mechanisms. These results are to be contrasted to the rate constants standardly calculated by approximate methods. © 19...

A new coercivity estimate on the spectral gap of the linearized Boltzmann collision operator for multiple species is proved. The assumptions on the collision kernels include hard and Maxwellian potentials under Grad’s angular cut-off condition. Two proofs are given: a non-constructive one, based on the decomposition of the collision operator into a compact and a coercive part, and a constructiv...

Binary fluorescence time series obtained from single-molecule imaging experiments can be used to infer protein binding kinetics, in particular, association and dissociation rate constants from waiting time statistics of fluorescence intensity changes. In many cases, rate constants inferred from fluorescence time series exhibit nonintuitive dependence on ligand concentration. Here, we examine se...

A number of phosphatidylcholine (PC) cations spanning a mass range of 400-1000 Da are investigated using electrospray ionization mass spectrometry coupled with traveling wave ion mobility spectrometry (TWIMS). A high correlation between mass and mobility is demonstrated with saturated phosphatidylcholine cations in N(2). A significant deviation from this mass-mobility correlation line is observ...

Symmetry breaking of the excited state of a linear quadrupolar acceptor-donor-acceptor molecule was investigated using time-resolved infrared spectroscopy in 55 solvents allowing the influence of several solute-solvent interactions to be examined separately. No symmetry breaking was found in nonpolar solvents irrespective of their refractive index, indicating that differences in dispersion inte...

Electron re-scattering in a strong laser field provides an important probe of molecular structure and processes, and can allow for time resolved study of nuclear and electronic dynamics at sub-femtosecond timescales with Angstrom spatial resolution. In such experiments a molecule is ionised in a strong, few cycle, laser field. The changes in sign of the laser field during the cycle can cause th...

Abstract Calculations are performed for electron collision with the methylene molecular ion C mathvariant="normal">H 2 + </mml:m...

Herein, we demonstrated the use of gas-phase intra-molecular reactions facilitated by collisional activation to investigate bi-molecular reactions with inherent low reactivity. Reactions between sulfinyl radicals (-SO˙) toward free thiol (-SH) were employed as a model system. A new reaction channel, i.e. sulfinyl exchange with thiol, was observed under beam-type collision-induced dissociation (...

Modification of a single carboxylate side chain in pepsin by 1,2-epoxy-3Qnitrophenoxy)propane abolished enzymic activity. The degree of inactivation was related to incorporation of the modifier in a 1: 1 molar ratio. The essential residue was an aspartic acid which is contained in the amino acid sequence Ile-Val-Asp-Thr-Gly-Ser-Ser-Asn. The pH rate profile of enzymic inactivation suggested the ...