Search results for "Physics::Chemical Physics"

Single molecule spectroscopy of multichromophoric assemblies

2003

We have investigated multichromophoric assemblies composed of a variable number of chromophores by single molecule spectroscopy. Specific spectral signatures have allowed to distinguish at the single molecule level between molecular dimers representing strong and weak electronic dipole-dipole coupling. By using fluorescence excitation spectroscopy at low temperature, the sharp purely electronic zero-phonon lines of single chromophores within a single dendrimer containing four chromophores could be isolated in the frequency domain.

Counterion-Mediated Crossing of the Cyanine Limit in Crystals and Fluid Solution: Bond Length Alternation and Spectral Broadening Unveiled by Quantum…

2020

Absorption spectra of cyanine⊕·Br⊖ salts show a remarkable solvent dependence in non/polar solvents, exhibiting narrow, sharp band shapes in dichloromethane but broad features in toluene; this chan...

Halogen bonding enhances nonlinear optical response in poled supramolecular polymers

2015

We demonstrate that halogen bonding strongly enhances the nonlinear optical response of poled supramolecular polymer systems. We compare three nonlinear optical chromophores with similar electronic structures but different bond-donating units, and show that both the type and the strength of the noncovalent interaction between the chromophores and the polymer matrix play their own distinctive roles in the optical nonlinearity of the systems. acceptedVersion Peer reviewed

Pulling Single Adsorbed Bottle-Brush Polymers off a Flat Surface: A Monte Carlo Simulation

2013

Force versus extension behavior of flexible chains and semiflexible bottle-brush polymers adsorbed from a good solvent on a planar substrate is studied by Monte Carlo simulation of the bond fluctua...

Modification of Polymers in Supercritical Carbon Dioxide

2003

The interaction of scFluids and polymers are governed by the intermolecular forces between solvent-solvent, solvent-polymer segment, and polymer segment-segment pairs. Because of its symmetry, within reasonable pressure values, CO2 does not have a dipole moment, but it does have a quadrupole moment significant over a much shorter distance than dipolar interactions. The quadrupole moment and the Lewis acidity of CO2 imparts to the carbon dioxide the peculiarity to be a solvent for selected classes of polymers like perfluorinated polyacrylates, polysiloxanes and polyether-polycarbonate diblock copolymers [1–3].

1988

The unperturbed dimensions parameter KΘ is one of the most important characteristics of a polymer chain. For binary systems (polymer/solvent) and mostly for ternary systems (polymer/solvent(1)/solvent(2)) the KΘ values show large discrepancies with respect to those under thetaconditions in a single solvent. These discrepancies can be explained by considering that the interaction parameter χ (and consequently the coil dimensions or the number of intramolecular contacts between polymer segments) changes with molecular weight M. Assuming this dependency, a modified Stockmayer-Fixman equation is proposed from which a unique value of KΘ for a given polymer, independent of M, is obtained. The use…

Deuteron n.m.r. in relation to the glass transition in polymers

1985

Abstract 2H n.m.r. is introduced as a tool for investigating slow molecular motion in the glass transition region of amorphous polymers. In particular, we compare 2H spin alignment echo spectra of chain deuterated polystyrene with models for restricted rotational Brownian motion. Molecular motion in the polystyrene-toluene system has been investigated by analysing 2H n.m.r. of partially deuterated polystyrene and toluene, respectively. The diluent mobility in the mixed glass has been decomposed into ‘solid’ and ‘liquid’ components where the respective average correlation times differ by more than 5 decades.

An Alternate Interpretation of Polymer/Solvent Jump Size Units for Free-Volume Diffusion Models

1996

Polystyrene/toluene mutual-diffusion coefficients have been measured as a function of temperature in the limit of infinite solvent dilution. The solvent to polymer jump size unit ratio (ξ) was determined from the Vrentas−Duda free-volume diffusion model for polymer self-diffusion and is in excellent agreement with values evaluated from solvent self- and binary mutual-diffusion coefficient data. Comparison of the free-volume model to a version of the Kirkwood−Riseman theory, modified for diffusion at infinite dilution under non-ϑ conditions, suggests that ξ follows the temperature dependence of the root-mean-squared end-to-end distance of the polystyrene and can be estimated without the use …

Insight in NLO Polymer Material Behavior from Langevin Dynamic Modeling of Chromophore Poling

2011

Calculation of chromophore polar order, i.e. the polarization of nonlinear optically (NLO) active polymers poled by external field, is challenging. One possible solution is to reproduce the orientation polarization of chromophores under external field using Langevin dynamics (LD) molecular modeling. The present work investigates the influence of chromophore dipole moment, density and field extent on NLO efficiency and polarization/relaxation dynamics. Results of simulations convince us, that the method is applicable for modeling real NLO polymers. In the spotlight of this investigation we would like to describe a NLO polymer as a “ferrofluid” where chromophores are active particles or elect…

Vibrational relaxation of matrix-isolated carboxylic acid dimers and monomers.

2009

Femtosecond mid-IR transient absorption spectroscopy was used to probe the vibrational dynamics of formic acid and acetic acid isolated in solid argon following excitation of the fundamental transition of the carbonyl stretching mode. Carboxylic acids form extremely stable H-bonded dimers, hindering the study of the monomeric species at equilibrium conditions. The low-temperature rare-gas matrix isolation technique allows for a unique control over aggregation enabling the study of the monomer vibrational dynamics, as well as the dynamics of two distinct dimer structures (cyclic and open chain). This study provides insight into the role of the methyl rotor and hydrogen bonding in the vibrati…