Molecular dynamics effects on luminescence properties of oligothiophene derivatives: a molecular mechanics-response theory study based on the CHARMM force field and density functional theory

CHARMM force field parameter values for a class of oligothiophene derivatives have been derived with reference to density functional theory/B3LYP potential energy surfaces. The force field parametrization of these luminescent conjugated polyelectrolytes includes the electronic ground state as well as the strongly light absorbing first excited state. In conjunction with quantum chemical response theory calculations of transition state properties, a molecular dynamical model of the Stokes shift is obtained. The theoretical model is benchmarked against experimental data recorded at room temperature which refer to sodium salts of p-HTAA and p-FTAA with distilled water as a solvent. For p-HTAA the theoretically predicted Stokes shift of 112 nm is in good agreement with the experimental result of 124 nm, given the approximations about exciton localization that were introduced to obtain a force field for the excited state.     

A perspective on nonresonant and resonant electronic response theory for time-dependent molecular properties

The development of electronic response theory in quantum chemistry has been reviewed, starting from the early 1970's and reaching the current state-of-the-art. The general theory has been applied to the calculation of a large number of spectroscopic parameters over the years, and it has been implemented for the majority of standard electronic structure methods. Two formulations of response theory, the Ehrenfest expectation value and the quasi-energy derivative formulation, have turned into leading alternatives for the derivation of computationally tractable expressions of response functions, and they are here reviewed with an attempt to, as far as possible, leave out technical details. A set of four steps are identified as common in derivations of response functions, and the two formulations are compared along this series of steps. Particular emphasis is given to the situation when the oscillation of the weak external electromagnetic field is in resonance with a transition frequency of the system. The formation of physically sound response functions in resonance regions of the spectrum is discussed in light of the causality condition and the Kramers-Kronig relations, and it is achieved in wave function theory by means of the introduction of relaxation parameters in a manner that mimics what one sees in density matrix theory. As a working example, equations are illustrated by their application to a two-state model for para-nitroaniline including the ground and the lowest charge-transfer state in the electric dipole approximation.     

Structure and dynamics of the fast lithium ion conductor "Li7La3Zr2O12"

The solid lithium-ion electrolyte "Li(7)La(3)Zr(2)O(12)" (LLZO) with a garnet-type structure has been prepared in the cubic and tetragonal modification following conventional ceramic syntheses routes. Without aluminium doping tetragonal LLZO was obtained, which shows a two orders of magnitude lower room temperature conductivity than the cubic modification. Small concentrations of Al in the order of 1 wt% were sufficient to stabilize the cubic phase, which is known as a fast lithium-ion conductor. The structure and ion dynamics of Al-doped cubic LLZO were studied by impedance spectroscopy, dc conductivity measurements, (6)Li and (7)Li NMR, XRD, neutron powder diffraction, and TEM precession electron diffraction. From the results we conclude that aluminium is incorporated in the garnet lattice on the tetrahedral 24d Li site, thus stabilizing the cubic LLZO modification. Simulations based on diffraction data show that even at the low temperature of 4 K the Li ions are blurred over various crystallographic sites. This strong Li ion disorder in cubic Al-stabilized LLZO contributes to the high conductivity observed. The Li jump rates and the activation energy probed by NMR are in very good agreement with the transport parameters obtained from electrical conductivity measurements. The activation energy E(a) characterizing long-range ion transport in the Al-stabilized cubic LLZO amounts to 0.34 eV. Total electric conductivities determined by ac impedance and a four point dc technique also agree very well and range from 1 × 10(-4) Scm(-1) to 4 × 10(-4) Scm(-1) depending on the Al content of the samples. The room temperature conductivity of Al-free tetragonal LLZO is about two orders of magnitude lower (2 × 10(-6) Scm(-1), E(a) = 0.49 eV activation energy). The electronic partial conductivity of cubic LLZO was measured using the Hebb-Wagner polarization technique. The electronic transference number t(e-) is of the order of 10(-7). Thus, cubic LLZO is an almost exclusive lithium ion conductor at ambient temperature.     

Fluorescence correlation spectroscopy evidence for structural heterogeneity in ionic liquids

In this work, we provide new experimental evidence for chain length-dependent self-aggregation in room temperature ionic liquids (RTILs) using fluorescence correlation spectroscopy (FCS). In studying a homologous series of N-alkyl-N-methylpyrrolidinium bis(trifluoromethylsulfonyl) imide, [C(n)MPy][Tf(2)N] RTILs of varying alkyl chain length (n = 3, 4, 6, 8, and 10), biphasic rhodamine 6G solute diffusion dynamics were observed; both the fast and slow diffusion coefficients decreased with increasing alkyl chain length, with the relative contribution from slower diffusion increasing for longer-chain [C(n)MPy][Tf(2)N]. We propose that the biphasic diffusion dynamics originate from self-aggregation of the nonpolar alkyl chains in the cationic [C(n)MPy](+).     

Chelatoaromaticity--existing: yes or no? An answer given by spatial magnetic properties (through space NMR shieldings--TSNMRS)

The spatial magnetic properties (through space NMR shieldings--TSNMRS) of metal complexes (with ligands such as acetylacetone, 3-hydroxy-pyran(4)one) and "metallobenzenes" have been calculated by the GIAO perturbation method and visualized as Iso-Chemical-Shielding Surfaces (ICSS) of various sizes and directions. The TSNMRS values, thus obtained, can be successfully employed to quantify and visualize partial aromaticity of the metallocyclic ring by comparison with the spatial magnetic properties of the corresponding non-complexed ligands in comparable structural and electronic situations, and benzene, respectively. Because anisotropy/ring current effects in (1)H NMR spectra proved to be the molecular response property of TSNMRS, the results obtained concerning partial "chelatoaromaticity" are experimentally ensured.     

Probing small molecule binding to amyloid fibrils

Much effort has focussed in recent years on probing the interactions of small molecules with amyloid fibrils and other protein aggregates. Understanding and control of such interactions are important for the development of diagnostic and therapeutic strategies in situations where protein aggregation is associated with disease. In this perspective article we give an overview over the toolbox of biophysical methods for the study of such amyloid-small molecule interactions. We discuss in detail two recently developed techniques within this framework: linear dichroism, a promising extension of the more traditional spectroscopic techniques, and biosensing methods, where surface-bound amyloid fibrils are exposed to solutions of small molecules. Both techniques rely on the measurement of physical properties that are very directly linked to the binding of small molecules to amyloid aggregates and therefore provide an attractive route to probe these important interactions.     

Synthesis,Photophysical, and Two‐Photon Absorption Properties of Elongated Phosphane Oxide and Sulfide Derivatives

A series of rod‐shaped and related three‐branched push–pull derivatives containing phosphane oxide or phosphane sulfide (PO or PS)—as an electron‐withdrawing group conjugated to electron‐donating groups, such as amino or ether groups, with a conjugated rod consisting of arylene–vinylene or arylene–ethynylene building blocks—were prepared. These compounds were efficiently synthesized by a Grignard reaction followed by Sonogashira coupling. Their photophysical properties including absorption, emission, time‐resolved fluorescence, and two‐photon absorption (TPA) were investigated with special attention to structure–property relationships. These fluorophores show high fluorescence quantum yields and solvent‐dependent experiments reveal that efficient intramolecular charge transfer occurs upon excitation, thereby leading to highly polar excited states, the polarity of which can be significantly enhanced by playing on the end groups and conjugated linker. Rod‐shaped and related three‐branched systems show similar fluorescence properties in agreement with excitation localization on one of the push–pull branches. By using stronger electron donors or replacing the arylene–ethynylene linkers with an arylene–vinylene one induces significant redshifts of both the low‐energy one‐photon absorption and TPA bands. Interestingly, a major enhancement in TPA responses is observed, whereas OPA intensities are only weakly affected. Similarly, phosphane oxide derivatives show similar OPA responses than the corresponding sulfides but their TPA responses are significantly larger. Finally, the electronic coupling between dipolar branches promoted by common PO or PS acceptor moieties induces either slight enhancement of the TPA responses or broadening of the TPA band in the near infrared (NIR) region. Such behavior markedly contrasts with triphenylamine‐core‐mediated coupling, which gives evidence for the different types of interactions between branches.