16 research outputs found
A theoretical simulation of the resonant Raman spectroscopy of the H2O⋯Cl2 and H2O⋯Br2 halogen-bonded complexes
The resonant Raman spectra of the H2O⋯Cl2 and H2O⋯Br2 halogen-bonded complexes have been studied in the framework of a 2-dimensional model previously used in the simulation of their UV-visible absorption spectra using time-dependent techniques. In addition to the vibrational progression along the dihalogen mode, a progression is observed along the intermolecular mode and its combination with the intramolecular one. The relative intensity of the inter to intramolecular vibrational progressions is about 15% for H2O⋯Cl2 and 33% for H2O⋯Br2. These results make resonant Raman spectra a potential tool for detecting the presence of halogen bonded complexes in condensed phase media such as clathrates and ice.Fil: Franklin Mergarejo, Ricardo. Université Paris Sud; Francia. Centre National de la Recherche Scientifique; Francia. InSTEC; Cuba. Consejo Nacional de Investigaciones CientÃficas y Técnicas; ArgentinaFil: Rubayo Soneira, Jesús. InSTEC; CubaFil: Halberstadt, Nadine. Université Paris Sud; Francia. Centre National de la Recherche Scientifique; FranciaFil: Janda, Kenneth C.. University of California at Irvine; Estados UnidosFil: Apkarian, V. Ara. University of California at Irvine; Estados Unido
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Orientation-Dependent Handedness of Chiral Plasmons on Nanosphere Dimers: How to Turn a Right Hand into a Left Hand
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Microscopy with a single-molecule scanning electrometer.
The vibrational spectrum of a single carbon monoxide molecule, adsorbed on the tip apex of a scanning tunneling microscope, is used to image electrostatic fields with submolecular spatial resolution. The method takes advantage of the vibrational Stark effect to image local electrostatic fields and the single-molecule sensitivity of tip-enhanced Raman scattering (TERS) to optically relay the signal. We apply the method to single metalloporphyrins adsorbed on Au(111) to image molecular charges, intramolecular polarization, local photoconductivity, atomically resolved hydrogen bonds, and surface electron density waves
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Junction Plasmon Driven Population Inversion of Molecular Vibrations: A Picosecond Surface-Enhanced Raman Spectroscopy Study.
Molecular surface-enhanced Raman spectra recorded at single plasmonic nanojunctions using a 7 ps pulse train exhibit vibrational up-pumping and population inversion. The process is assigned to plasmon-driven, dark, impulsive electron-vibration (e-v) excitation. Both optical (Raman) pumping and hot-electron mediated excitation can be rejected by the characteristic spectra, which allow the simultaneous measurement of vibrational temperature of the molecules and electronic temperature of the metal. Vibrational populations are determined from anti-Stokes to Stokes intensity ratios, while the electron temperature is obtained from the anti-Stokes branch of the electronic Raman scattering continuum. Population inversion survives in high-frequency vibrations that effectively decouple from the metal
Orientation-Dependent Handedness of Chiral Plasmons on Nanosphere Dimers: How to Turn a Right Hand into a Left Hand
Optical activity,
which is used as a discriminator of chiral enantiomers,
is demonstrated to be orientation dependent on individual, and nominally
achiral, plasmonic nanosphere dimers. Through measurements of their
giant Raman optical activity, we demonstrate that L/R-handed enantiomers
can be continuously turned into their R/L-handed mirror images without
passing through an achiral state. The primitive uniaxial multipolar
response, with demonstrable broken parity and time reversal symmetry,
reproduces the observations as resonant Raman scattering on plasmons
that carry angular momentum. The analysis underscores that chirality
does not have a quantitative continuous measure and recognizes the
manipulation of superpositions of multipolar plasmons as a paradigm
for novel optical materials with artificial magnetism
Spectroscopic Signatures of Halogens in Clathrate Hydrate Cages. 2. Iodine
UV-vis and Raman spectroscopy were used to study iodine molecules trapped in sII clathrate hydrate structures stabilized by THF, CH2Cl2, or CHCl3. The spectra show that the environment for iodine inside the water cage is significantly less perturbed than either in aqueous solution or in amorphous water-ice. The resonance Raman progression of I2 in THF clathrate hydrate can be observed up to V) 6 when excited at 532 nm. The extracted vibrational frequency öe) 214 ( 1 cm-1 is the same as that of the free molecule to within experimental error. At the same time, the UV-vis absorption spectrum of I2 in the sII hydrate exhibits a relatively large, 1440 cm-1, blue-shift. This is mainly ascribed to the differential solvation of the I2 electronic states. We conclude that iodine in sII hydrate resides in a 51264 cavity, in which the ground-state I2 potential is not significantly perturbed by the hydrate lattice. In contrast, in water and in ice, the valence absorption band of I2 is dramatically broadened and blue-shifted by 3000 cm-1, and the resonance Raman scattering is effectively quenched. These observations are shown to be consistent with a strong interaction between water molecule and iodine through the lone pair of electrons on water as in the case of bromine in the same media. The results presented here, and the stability of other halogen hydrates, were used to test the predictions of simple models and force-field calculations of the host cage-guest association energy