Fluorescence lifetimes and correlated photon statistics from single CdSe/oligo(phenylene vinylene) composite nanostructures.

We present measurements of fluorescence intensity trajectories and associated excited-state decay times from individual CdSe/oligo(phenylene vinylene) (CdSe-OPV) quantum dot nanostructures using time-tagged, time-resolved (TTTR) photon counting techniques. We find that fluorescence decay times for the quantum dot emitter in these composite systems are at least an order of magnitude shorter than ZnS-capped CdSe quantum dot systems. We show that both the blinking suppression and associated lifetime/count rate behavior can be described by a modified version of the diffusive reaction coordinate model which couples slow fluctuations in quantum dot electron (1Se, 1Pe) energies to Auger-assisted hole trapping processes, hence modifying both blinking statistics and excited-state decay rates.

Blinking suppression and intensity recurrences in single CdSe-oligo(phenylene vinylene) nanostructures: experiment and kinetic model.

We report time-resolved single molecule fluorescence imaging of individual CdSe quantum dots that are functionalized with oligomeric conjugated organic ligands. The fluorescence intensity trajectories from these composite nanostructures display both a strong degree of blinking suppression and intensity fluctuations with characteristic recurrence times on the order of 10-60 s. In addition, fluorescence decay rate measurements of individual hybrid nanostructures indicate significantly modified non-radiative quantum dot decay rates relative to conventional ZnS-capped CdSe quantum dots. We show that a modified diffusive reaction coordinate model with slow fluctuations in quantum dot electron energies (1S(e), 1P(e)) can reproduce the experimentally observed behaviour.

Infrared spectrum and structural assignment of the water trimer anion.

The bending vibrational spectrum of the perdeutero isotopomer of the water trimer anion has been measured and compared with spectra calculated using the MP2, CCSD, and Becke3LYP electronic structure methods. Due to its low electron binding energy (approximately 150 meV), only the OD bending region of the IR spectrum of (D2O)3(-) is accessible experimentally, with electron ejection dominating at higher photon energies. The calculated spectrum of the isomer having three water molecules arranged in a chain agrees best with the experimental spectrum. In the chain isomer, the excess electron is bound to the terminal water monomer with two dangling OH groups. This is consistent with the electron binding mechanism established previously for the (H2O)n(-) (n = 2, 4-6) anions.

Negative ions of ethylene sulfite.

The formation of negative ions in molecular beams of ethylene sulfite (ES, alternately called glycol sulfite or ethylene glycol, C(2)H(4)SO(3)) molecules has been studied using both Rydberg electron transfer (RET) and free electron attachment methods. RET experiments with jet-cooled ES show an unexpected broad profile of anion formation as a function of the effective quantum number (n(*)) of the excited rubidium atoms, with peaks at n(max)(*) approximately 13.5 and 16.8. The peak at n(max)(*) approximately 16.8 corresponds to an expected dipole-bound anion with an electron binding energy of 8.5 meV. It is speculated that the peak at n(max)(*) approximately 13.5 derives from the formation of a distorted C(2)H(4)SO(3)(-) ion. We suggest that quasifree electron attachment promotes the breaking of one ring bond giving a long-lived acyclic anion and term this process incomplete dissociative electron attachment. Theoretical calculations of plausible ionic structures are presented and discussed. Electron beam studies of ES reveal the presence of multiple dissociative attachment channels, with the dominant fragment, SO(2)(-), peaking at 1.3 eV and much weaker signals due to SO(3)(-), SO(-), and (ES-H)(-) peaking at 1.5, 1.7, and 0.9 eV, respectively. All of these products appear to originate from a broad temporary negative ion resonance centered at approximately 1.4 eV.

An infrared investigation of the (CO2)n- clusters: core ion switching from both the ion and solvent perspectives.

The (CO2)n- clusters are thought to accommodate the excess electron by forming a localized molecular anion, or "core ion", solvated by the remaining, largely neutral CO2 molecules. Earlier studies interpreted discontinuities in the (CO2)n- photoelectron spectra to indicate that both the CO2- and C2O4- species were present in a size-dependent fashion. Here we use vibrational predissociation spectroscopy to unambiguously establish the molecular structures of the core ions in the 2 < or = n < or = 17 size range. Spectra are reported in the 2300-3800 cm(-1) region, which allows us to independently monitor the contribution of each ion through its characteristic overtone and combination bands. These signature bands are observed to be essentially intact in the larger clusters, establishing that the CO2- and C2O4- molecular ions are indeed the only electron accommodation modes at play. The size dependence of the core ion suggested in earlier analyses of the photoelectron spectra is largely confirmed, although both species are present over a range of clusters near the expected critical cluster sizes, as opposed to the prompt changes inferred earlier. Perturbations in the bands associated with the nominally neutral CO2 "solvent" molecules are correlated with the changes in the molecular structure of the core ion. These observations are discussed in the context of a diabatic model for electron delocalization over the CO2 dimer. In this picture, the driving force leading to the transient formation of the monomer ion is traced to the solvent asymmetry inherent in an incomplete coordination shell.

Infrared signature of structures associated with the H+(H2O)n (n = 6 to 27) clusters.

We report the OH stretching vibrational spectra of size-selected H+(H2O)n clusters through the region of the pronounced "magic number" at n = 21 in the cluster distribution. Sharp features are observed in the spectra and assigned to excitation of the dangling OH groups throughout the size range 6

Long-range electron binding to quadrupolar molecules.

An excess electron can be bound to a molecule in a very diffuse orbital as a result of the long-range contributions of the molecular electrostatic field. Following a systematic search, we report experimental evidence that quadrupole binding occurs for the trans-succinonitrile molecule (EA=20+/-2 meV), while the gauche-succinonitrile conformer supports a dipole-bound anion state (EA=108+/-10 meV). Theoretical calculations at the DFT/B3LYP level support these interpretations and give electron affinities of 20 and 138 meV, respectively.