Biomedical subjects

Nathan I Hammer

Publications and source records attributed to Nathan I Hammer.

9 recordsLinked to original sources

PubMed2006

Observation of enhanced energy transfer in individual quantum dot-oligophenylene vinylene nanostructures.

The temporal and spectral properties of luminescence from individual CdSe quantum dot-oligophenylene vinylene nanostructures (single quantum dots with conjugated organic ligands coordinated to the surface) are profoundly modified relative to blended films of the same components. These kinds of composite quantum dot-conjugated organic systems have attracted significant interest as a way to improve efficiency in photovoltaic device applications. By direct functionalization of the dot surface with the conjugated organic ligands, we realize a significant enhancement in energy transfer and luminescence stability.

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PubMed2005

Vibrational predissociation spectroscopy of the (H2O)(6-21)- clusters in the OH stretching region: evolution of the excess electron-binding signature into the intermediate cluster size regime.

We report vibrational predissociation spectra of the (H2O)n- cluster ions in the OH stretching region to determine whether the spectral signature of the electron-binding motif identified in the smaller clusters [Hammer et al. Science 306, 675 (2004)] continues to be important in the intermediate size regime (n = 7-21). This signature consists of a redshifted doublet that dominates the OH stretching region, and has been traced primarily to the excitation of a single water molecule residing in a double H-bond acceptor (AA) binding site, oriented with both of its H atoms pointing toward the excess electron cloud. Strong absorption near the characteristic AA doublet is found to persist in the spectra of the larger clusters, but the pattern evolves into a broadened triplet around n = 11. A single free OH feature associated with dangling hydrogen atoms on the cluster surface is observed to emerge for n > or = 15, in sharp contrast to the multiplet pattern of unbonded OH stretches displayed by the H+(H2O)n clusters throughout the n = 2-29 range. We also explore the vibration-electronic coupling associated with normal-mode displacements of the AA molecule that most strongly interact with the excess electron. Specifically, electronic structure calculations on the hexamer anion indicate that displacement along the -OH2 symmetric stretching mode dramatically distorts the excess electron cloud, thus accounting for the anomalously large oscillator strength of the AA water stretching vibrations. We also discuss these vibronic interactions in the context of a possible relaxation mechanism for the excited electronic states involving the excess electron.

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PubMed2005

Mid-infrared characterization of the NH4 +(H2O)n clusters in the neighborhood of the n=20 "magic" number.

Vibrational predissociation spectra are reported for size-selected NH4+ (H2O)n clusters (n=5-22) in the 2500-3900 cm(-1) region. We concentrate on the sharp free OH stretching bands to deduce the local H-bonding configurations of water molecules on the cluster surface. As in the spectra of the protonated water clusters, the free OH bands in NH4+ (H2O)n evolve from a quartet at small sizes (n<7), to a doublet around n=9, and then to a single peak at the n=20 magic number cluster, before the doublet re-emerges at larger sizes. This spectral simplification at the magic number cluster mirrors that found earlier in the H+(H2O)n clusters. We characterize the likely structures at play for the n=19 and 20 clusters with electronic structure calculations. The most stable form of the n=20 cluster is predicted to have a surface-solvated NH4+ ion that lies considerably lower in energy than isomers with the NH4+ in the interior.

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PubMed2005

The vibrational predissociation spectra of the H5O2 +RGn(RG = Ar,Ne) clusters: correlation of the solvent perturbations in the free OH and shared proton transitions of the Zundel ion.

Predissociation spectra of the H(5)O(2) (+)RG(n)(RG = Ar,Ne) cluster ions are reported in energy regions corresponding to both the OH stretching (3350-3850 cm(-1)) and shared proton (850-1950 cm(-1)) vibrations. The two free OH stretching bands displayed by the Ne complex are quite close to the band origins identified earlier in bare H(5)O(2) (+) [L. I. Yeh, M. Okumura, J. D. Myers, J. M. Price, and Y. T. Lee, J. Chem. Phys. 91, 7319 (1989)], indicating that the symmetrical H(5)O(2) (+) "Zundel" ion remains largely intact in H(5)O(2) (+)Ne. The low-energy spectrum of the Ne complex is simpler than that observed previously for H(5)O(2) (+)Ar, and is dominated by two sharp transitions at 928 and 1047 cm(-1), with a weaker feature at 1763 cm(-1). The H(5)O(2) (+)Ar(n),n = 1-5 spectra generally exhibit complex band structures reflecting solvent-induced symmetry breaking of the Zundel core ion. The extent of solvent perturbation is evaluated with electronic structure calculations, which predict that the rare gas atoms should attach to the spectator OH groups of H(5)O(2) (+) rather than to the shared proton. In the asymmetric complexes, the shared proton resides closer to the more heavily solvated water molecule, leading to redshifts in the rare gas atom-solvated OH stretches and to blueshifts in the shared proton vibrations. The experimental spectra are compared with recent full-dimensional vibrational calculations (diffusion Monte Carlo and multimode/vibrational configuration interaction) on H(5)O(2) (+). These results are consistent with assignment of the strong low-energy bands in the H(5)O(2) (+)Ne spectrum to the vibration of the shared proton mostly along the O-O axis, with the 1763 cm(-1) band traced primarily to the out-of-phase, intramolecular bending vibrations of the two water molecules.

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PubMed2005

Spectral signatures of hydrated proton vibrations in water clusters.

The ease with which the pH of water is measured obscures the fact that there is presently no clear molecular description for the hydrated proton. The mid-infrared spectrum of bulk aqueous acid, for example, is too diffuse to establish the roles of the putative Eigen (H3O+) and Zundel (H5O2+) ion cores. To expose the local environment of the excess charge, we report how the vibrational spectrum of protonated water clusters evolves in the size range from 2 to 11 water molecules. Signature bands indicating embedded Eigen or Zundel limiting forms are observed in all of the spectra with the exception of the three- and five-membered clusters. These unique species display bands appearing at intermediate energies, reflecting asymmetric solvation of the core ion. Taken together, the data reveal the pronounced spectral impact of subtle changes in the hydration environment.

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PubMed2005

Isotope effects in dipole-bound anions of acetone.

Precision measurements using the Rydberg charge-exchange and electric field-detachment methods find that the dipole-bound electron affinity (EA) of acetone (C3H6O) is 55+/-10 mueV greater than for deuterated acetone (C3D6O). The result agrees well with a theoretical prediction obtained with high-level electronic-structure and anharmonic vibrational calculations. The dipole moments calculated for the vibrationally averaged structures of C3H6O and C3D6O show that the isotope effect (2% reduction) on the EA of acetone is mainly due to a slight reduction (0.5%) of the average dipole moment upon deuteration.

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PubMed2004

How do small water clusters bind an excess electron?

The arrangement of water molecules around a hydrated electron has eluded explanation for more than 40 years. Here we report sharp vibrational bands for small gas-phase water cluster anions, (H2O)(4-6)- and (D2O)(4-6)-. Analysis of these bands reveals a detailed picture of the diffuse electron-binding site. The electron is closely associated with a single water molecule attached to the supporting network through a double H-bond acceptor motif. The local OH stretching bands of this molecule are dramatically distorted in the pentamer and smaller clusters because the excited vibrational levels are strongly coupled to the electron continuum. The vibration-to-electronic energy transfer rates, as revealed by line shape analysis, are mode-specific and remarkably fast, with the symmetric stretching mode surviving for less than 10 vibrational periods [50 fs in (H2O)4-].

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PubMed2004

Preparation and photoelectron spectrum of the glycine molecular anion: assignment to a dipole-bound electron species with a high-dipole moment, non-zwitterionic form of the neutral core.

We report the gas-phase preparation of negatively charged glycine as well as the Gly(H(2)O)(1,2) (-) complexes by entrainment of the neutral precursor into an ionized supersonic expansion tuned to optimize the (H(2)O)(n) (-)Ar(m) clusters. The photoelectron spectrum of Gly(-) displays the signature of a dipole-bound species, with sufficient vibrational fine structure to characterize the core neutral as a higher energy, non-zwitterionic isomer of the amino acid.

Anions↗

PubMed2004

Dipole-bound anions of highly polar molecules: ethylene carbonate and vinylene carbonate.

Results of experimental and theoretical studies of dipole-bound negative ions of the highly polar molecules ethylene carbonate (EC, C3H4O3, mu=5.35 D) and vinylene carbonate (VC, C3H2O3, mu=4.55 D) are presented. These negative ions are prepared in Rydberg electron transfer (RET) reactions in which rubidium (Rb) atoms, excited to ns or nd Rydberg states, collide with EC or VC molecules to produce EC- or VC- ions. In both cases ions are produced only when the Rb atoms are excited to states described by a relatively narrow range of effective principal quantum numbers, n*; the greatest yields of EC- and VC- are obtained for n*(max)=9.0+/-0.5 and 11.6+/-0.5, respectively. Charge transfer from low-lying Rydberg states of Rb is characteristic of a large excess electron binding energy (Eb) of the neutral parent; employing the previously derived empirical relationship Eb=23/n*(max)(2.8) eV, the electron binding energies are estimated to be 49+/-8 meV for EC and 24+/-3 meV for VC. Electron photodetachment studies of EC- show that the excess electron is bound by 49+/-5 meV, in excellent agreement with the RET results, lending credibility to the empirical relationship between Eb and n*(max). Vertical electron affinities for EC and VC are computed employing aug-cc-pVDZ atom-centered basis sets supplemented with a (5s5p) set of diffuse Gaussian primitives to support the dipole-bound electron; at the CCSD(T) level of theory the computed electron affinities are 40.9 and 20.1 meV for EC and VC, respectively.

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