With the large dye molecules employed in typical studies of solvation dynamics, it is often difficult to separate the intramolecular relaxation of the dye from the relaxation associated with dynamic solvation. One way to avoid this difficulty is to study solvation dynamics using an atom as the solvation probe; because atoms have only electronic degrees of freedom, all of the observed spectrosco...

The recently discovered O(d; d) symmetry of the space of (slowly-varying) cosmo-logical string vacua in d + 1 dimensions is shown to be preserved in the presence of bulk string matter. The existence of O(d; d) conserved currents allows all the equations of string cosmology to be reduced to rst-order diierential equations. The perfect-uid approximation is not invariant under O(d; d) transformati...

Studying solvation of a large molecule on an atomic level is challenging because of the transient character and inhomogeneity of hydrogen bonding in liquid water. We studied water clusters of a protonated macrocyclic decapeptide, gramicidin S, which were prepared in the gas phase and then cooled to cryogenic temperatures. The experiment spectroscopically tracked fine structural changes of the c...

Implicit solvent models are increasingly popular for estimating aqueous solvation (hydration) free energies in molecular simulations and other applications. In many cases, parameters for these models are derived to reproduce experimental values for small molecule hydration free energies. Often, these hydration free energies are computed for a single solute conformation, neglecting solute confor...

The complexes of the fluorescence probe coumarin 153 with apomyoglobin and apoleghemoglobin are used as model systems to study solvation dynamics in proteins. Time-resolved Stokes shift experiments are compared with molecular dynamics simulations, and very good agreement is obtained. The solvation of the coumarin probe is very rapid with approximately 60% occurring within 300 fs and is attribut...

Preferential solvation in aromatic nucleophilic substitution reactions is discussed using a kinetic study complemented with quantum chemical calculations. The model system is the reaction of a series of secondary alicyclic amines toward phenyl 2,4,6-trinitrophenyl ether in aqueous ethanol mixtures of different compositions. From solvent effect studies, it is found that only piperidine is sensit...

Solvation and rotational dynamics of 4-aminophthalimide (4AP) in four ionic liquids (ILs) are measured using a combination of fluorescence upconversion spectroscopy and time-correlated single photon counting. These data are compared with previously reported data for coumarin 153 (C153) to investigate the probe dependence of solvation dynamics. No fast component (<15 ps) in the fluorescence anis...

The exact interaction between Au cores and surface ligands remains largely unknown because of the complexity of the structure and chemistry of ligand/Au-core interfaces in ligand-protected Au nanoclusters (AuNCs), which are commonly found in many organic-inorganic complexes. Here, femtosecond transient absorption measurement of the excited-state dynamics of a newly synthesized phosphine-protect...

Simplified models and empirical potentials are being increasingly used for the analysis of proteins, frequently augmenting or replacing molecular mechanics approaches. Recent folding simulations have employed potentials that, in addition to terms assuring proper polypeptide geometry, include only two noncovalent effects-hydrogen bonding and hydrophobicity, with extremely simple approximations t...