178 research outputs found
CO adsorption on neutral iridium clusters
The adsorption of carbon monoxide on neutral iridium clusters in the size
range of n = 3 to 21 atoms is investigated with infrared multiple photon
dissociation spectroscopy. For each cluster size only a single v(CO) band is
present with frequencies in the range between 1962 cm-1 (n = 8) and 1985 cm-1
(n = 18) which can be attributed to an atop binding geometry. This behaviour is
compared to the CO binding geometries on clusters of other group 9 and 10
transition metals as well as to that on extended surfaces. The preference of Ir
for atop binding is rationalized by relativistic effects on the electronic
structure of the later 5d metals
Optical creation of vibrational intrinsic localized modes in anharmonic lattices with realistic interatomic potentials
Using an efficient optimal control scheme to determine the exciting fields,
we theoretically demonstrate the optical creation of vibrational intrinsic
localized modes (ILMs) in anharmonic perfect lattices with realistic
interatomic potentials. For systems with finite size, we show that ILMs can be
excited directly by applying a sequence of femtosecond visible laser pulses at
THz repetition rates. For periodic lattices, ILMs can be created indirectly via
decay of an unstable extended lattice mode which is excited optically either by
a sequence of pulses as described above or by a single picosecond far-infrared
laser pulse with linearly chirped frequency. In light of recent advances in
experimental laser pulse shaping capabilities, the approach is experimentally
promising.Comment: 20 pages, 7 eps figures. Accepted, Phys. Rev.
Secondary structure of Ac-Ala-LysH polyalanine peptides (=5,10,15) in vacuo: Helical or not?
The polyalanine-based peptide series Ac-Ala_n-LysH+ (n=5-20) is a prime
example that a secondary structure motif which is well-known from the solution
phase (here: helices) can be formed in vacuo. We here revisit this conclusion
for n=5,10,15, using density-functional theory (van der Waals corrected
generalized gradient approximation), and gas-phase infrared vibrational
spectroscopy. For the longer molecules (n=10,15) \alpha-helical models provide
good qualitative agreement (theory vs. experiment) already in the harmonic
approximation. For n=5, the lowest energy conformer is not a simple helix, but
competes closely with \alpha-helical motifs at 300K. Close agreement between
infrared spectra from experiment and ab initio molecular dynamics (including
anharmonic effects) supports our findings.Comment: 4 pages, 4 figures, Submitted to JPC Letter
Observation of band structure and density of states effects in Co-based magnetic tunnel junctions
Utilizing Co/AlO/Co magnetic tunnel junctions (MTJs) with Co
electrodes of different crystalline phases, a clear relationship between
electrode structure and junction transport properties is presented. For
junctions with one fcc(111) textured and one polycrystalline (poly-phase and
poly-directional) Co electrode, a strong asymmetry is observed in the
magnetotransport properties, while when both electrodes are polycrystalline the
magnetotransport is essentially symmetric. These observations are successfully
explained within a model based on ballistic tunneling between the calculated
band structures (DOS) of fcc-Co and hcp-Co.Comment: 4 pages, 3 figures, submitted to Phys. Rev. Let
Infrared Multiple Photon Dissociation Action Spectroscopy and Theoretical Studies of Diethyl Phosphate Complexes: Effects of Protonation and Sodium Cationization on Structure
The gas-phase structures of deprotonated, protonated, and sodium-cationized complexes of diethyl phosphate (DEP) including [DEP − H]−, [DEP + H]+, [DEP + Na]+, and [DEP − H + 2Na]+ are examined via infrared multiple photon dissociation (IRMPD) action spectroscopy using tunable IR radiation generated by a free electron laser, a Fourier transform ion cyclotron resonance mass spectrometer (FT-ICR MS) with an electrospray ionization (ESI) source, and theoretical electronic structure calculations. Measured IRMPD spectra are compared to linear IR spectra calculated at the B3LYP/6-31G(d,p) level of theory to identify the structures accessed in the experimental studies. For comparison, theoretical studies of neutral complexes are also performed. These experiments and calculations suggest that specific geometric changes occur upon the binding of protons and/or sodium cations, including changes correlating to nucleic acid backbone geometry, specifically P–O bond lengths and ∠OPO bond angles. Information from these observations may be used to gain insight into the structures of more complex systems, such as nucleotides and solvated nucleic acids
Action spectroscopy of gas-phase carboxylate anions by multiple photon IR electron detachment/attachment
We report on a form of gas-phase anion action spectroscopy based on infrared
multiple photon electron detachment and subsequent capture of the free
electrons by a neutral electron scavenger in a Fourier Transform Ion Cyclotron
Resonance (FTICR) mass spectrometer. This method allows one to obtain
background-free spectra of strongly bound anions, for which no dissociation
channels are observed. The first gas-phase spectra of acetate and propionate
are presented using SF6 as electron scavenger and a free electron laser as
source of intense and tunable infrared radiation. To validate the method, we
compare infrared spectra obtained through multiple photon electron
detachment/attachment and multiple photon dissociation for the benzoate anion.
In addition, different electron acceptors are used, comparing both associative
and dissociative electron capture. The relative energies of dissociation (by
CO2 loss) and electron detachment are investigated for all three anions by DFT
and CCSD(T) methods. DFT calculations are also employed to predict vibrational
frequencies, which provide a good fit to the infrared spectra observed. The
frequencies of the symmetric and antisymmetric carboxylate stretching modes for
the aliphatic carboxylates are compared to those previously observed in
condensed-phase IR spectra and to those reported for gas-phase benzoate,
showing a strong influence of the solution environment and a slight substituent
effect on the antisymmetric stretch.Comment: Revised version, Submitted to J Phys Chem
Spectroscopic Evidence for an Oxazolone Structure in Anionic b-Type Peptide Fragments
Infrared spectra of anionic b-type fragments generated by collision induced dissociation (CID) from deprotonated peptides are reported. Spectra of the b2 fragments of deprotonated AlaAlaAla and AlaTyrAla have been recorded over the 800–1800 cm–1 spectral range by multiple-photon dissociation (MPD) spectroscopy using an FTICR mass spectrometer in combination with the free electron laser FELIX. Structural characterization of the b-type fragments is accomplished by comparison with density functional theory calculated spectra at the B3LYP/6-31++G(d,p) level for different isomeric structures. Although diketopiperazine structures represent the energetically lowest isomers, the IR spectra suggest an oxazolone structure for the b2 fragments of both peptides. Deprotonation is shown to occur on the oxazolone α-carbon, which leads to a conjugated structure in which the negative charge is practically delocalized over the entire oxazolone ring, providing enhanced gas-phase stability
First lasing of the Jefferson Lab IR Demo FEL
As reported previously [1], Jefferson Lab is building a free-electron laser capable of generating a continuous wave kilowatt laser beam. The driver-accelerator consists of a superconducting, energy-recovery accelerator. The initial stage of the program was to produce over 100 W of average power with no recirculation. In order to provide maximum gain the initial wavelength was chosen to be 5 mu-m and the initial beam energy was chosen to be 38.5 MeV. On June 17, 1998, the laser produced 155 Watts cw power at the laser output with a 98% reflective output coupler. On July 28th, 311 Watts cw power was obtained using a 90% reflective output coupler. A summary of the commissioning activities to date as well as some novel lasing results will be summarized in this paper. Present work is concentrated on optimizing lasing at 5 mu-m, obtaining lasing at 3 mu-m, and commissioning the recirculation transport in preparation for kilowatt lasing this fall
- …