0000000000077615
AUTHOR
V. A. Apkarian
showing 7 related works from this author
Chemically Selective Imaging of Individual Bonds through Scanning Electron Energy-Loss Spectroscopy: Disulfide Bridges Linking Gold Nanoclusters
2020
As proof-of-principle of chemically selective, spatially resolved imaging of individual bonds, we carry out electron energy-loss spectroscopy in a scanning transmission electron microscopy instrument on atomically precise, thiolate-coated gold nanoclusters linked with 5,5'-bis(mercaptomethyl)-2,2'-bipyridine dithiol ligands. The images allow the identification of bridging disulfide bonds (R-S-S-R) between clusters, and X-ray photoelectron spectra support the finding.
Time-resolved coherent anti-Stokes Raman-scattering measurements of I2 in solid Kr: vibrational dephasing on the ground electronic state at 2.6-32 K.
2005
Time-resolved coherent anti-Stokes Raman-scattering (CARS) measurements are carried out for iodine (I2) in solid krypton matrices. The dependence of vibrational dephasing time on temperature and vibrational quantum number v is studied. The v dependence is approximately quadratic, while the temperature dependence of both vibrational dephasing and spectral shift, although weak, fits the exponential form characteristic of dephasing by pseudolocal phonons. The analysis of the data indicates that the frequency of the pseudolocal phonons is approximately 30 cm(-1). The longest dephasing times are observed for v = 2 being approximately 300 ps and limited by inhomogeneous broadening. An increase in…
Observation and analysis of Fano-like lineshapes in the Raman spectra of molecules adsorbed at metal interfaces
2015
Surface enhanced Raman spectra from molecules (bipyridyl ethylene) adsorbed on gold dumbells are observed to become increasingly asymmetric (Fano-like) at higher incident light intensity. The electronic temperature (inferred from the anti-Stokes (AS) electronic Raman signal increases at the same time while no vibrational AS scattering is seen. These observations are analyzed by assuming that the molecule-metal coupling contains an intensity dependent contribution (resulting from light-induced charge transfer transitions as well as renormalization of the molecule metal tunneling barrier). We find that interference between vibrational and electronic inelastic scattering routes is possible in …
Seeing a single molecule vibrate through time-resolved coherent anti-Stokes Raman scattering
2014
The vibrations of the chemical bonds of a single molecule are observed by employing time-resolved coherent anti-Stokes Raman scattering. A gold nanoantenna is used to enhance the signal from the molecule.
Time-domain analysis of electronic spectra in superfluid 4He
2004
Abstract Electronic absorption spectra of impurities in superfluid helium is developed in time domain, using time-dependent density functional theory to describe liquid 4 He and time-dependent perturbation theory to describe the electronic degrees of freedom of the impurity. Angularly isotropic potentials are used to describe the molecule–helium interactions in the ground and excited electronic states. The calculations rationalize experimentally observed phonon side-bands in 4 He droplets and in bulk helium, and allow assignments of spectral features to specific motions of the liquid.
Orbiting Orbitals: Visualization of Vi-Bronic Motion at a Conical Intersection
2013
The Jahn-Teller (JT) active unpaired electron of single metalloporphyrin radical anions is imaged through scanning tunneling microscopy. It is demonstrated that the electron is delocalized over the porphyrin macrocycle and its topographic image is determined by vibronic motion: the orbital of the electron adiabatically follows the zero-point pseudorotation of skeletal deformations. Transformation of the polar graphs of the observed images allows visualization of the adiabatic vibrational density to which the electron is coupled. The vibronic potential at the conical intersection is visualized and the half-integer angular momentum characteristic of the Berry phase is revealed in the radial f…
Injection of atoms and molecules in a superfluid helium fountain: Cu and Cu2He(n) (n = 1, ..., ∞).
2011
We introduce an experimental platform designed around a thermomechanical helium fountain, which is aimed at investigating spectroscopy and dynamics of atoms and molecules in the superfluid and at its vapor interface. Laser ablation of copper, efficient cooling and transport of Cu and Cu(2) through helium vapor (1.5 K < T < 20 K), formation of linear and T-shaped Cu(2)-He complexes, and their continuous evolution into large Cu(2)-He(n) clusters and droplets are among the processes that are illustrated. Reflection is the dominant quantum scattering channel of translationally cold copper atoms (T = 1.7 K) at the fountain interface. Cu(2) dimers mainly travel through the fountain unimpeded. How…