3,405 research outputs found
Theoretical study of molecular electronic excitations and optical transitions of C60
We report results on ab initio calculations of excited states of the
fullerene molecule by using configuration interaction (CI) approach with singly
excited determinants (SCI). We have used both the experimental geometry and the
one optimized by the density functional method and worked with basis sets at
the cc-pVTZ and aug-cc-pVTZ level. Contrary to the early SCI semiempirical
calculations, we find that two lowest electron
optical lines are situated at relatively high energies of ~5.8 eV (214 nm) and
~6.3 eV (197 nm). These two lines originate from two transitions: from HOMO to (LUMO+1) () and from (HOMO--1)
to LUMO (). The lowest molecular excitation, which is the level, is found at ~2.5 eV. Inclusion of doubly excited determinants
(SDCI) leads only to minor corrections to this picture. We discuss possible
assignment of absorption bands at energies smaller than 5.8 eV (or
larger than 214 nm).Comment: 6 pages, 1 figure, 9 Table
A joint time-dependent density-functional theory for excited states of electronic systems in solution
We present a novel joint time-dependent density-functional theory for the
description of solute-solvent systems in time-dependent external potentials.
Starting with the exact quantum-mechanical action functional for both electrons
and nuclei, we systematically eliminate solvent degrees of freedom and thus
arrive at coarse-grained action functionals which retain the highly accurate
\emph{ab initio} description for the solute and are, in principle, exact. This
procedure allows us to examine approximations underlying popular embedding
theories for excited states. Finally, we introduce a novel approximate action
functional for the solute-water system and compute the solvato-chromic shift of
the lowest singlet excited state of formaldehyde in aqueous solution, which is
in good agreement with experimental findings.Comment: 11 page
Detection of interstellar CH_3
Observations with the Short Wavelength Spectrometer (SWS) onboard the {\it
Infrared Space Observatory} (ISO) have led to the first detection of the methyl
radical in the interstellar medium. The branch at 16.5
m and the (0) line at 16.0 m have been unambiguously detected
toward the Galactic center SgrA. The analysis of the measured bands gives a
column density of (8.02.4) cm and an excitation
temperature of K. Gaseous at a similarly low excitation
temperature and are detected for the same line of sight. Using
constraints on the column density obtained from and
visual extinction, the inferred abundance is
. The chemically related
molecule is not detected, but the pure rotational lines of are seen
with the Long Wavelength Spectrometer (LWS). The absolute abundances and the
and ratios are inconsistent with published
pure gas-phase models of dense clouds. The data require a mix of diffuse and
translucent clouds with different densities and extinctions, and/or the
development of translucent models in which gas-grain chemistry, freeze-out and
reactions of with polycyclic aromatic hydrocarbons and solid
aliphatic material are included.Comment: 2 figures. ApJL, Accepte
[NiFe]-hydrogenase maturation in vitro: analysis of the roles of the HybG and HypD accessory proteins
[NiFe]-hydrogenases (Hyd) bind a nickel-iron-based cofactor. The Fe ion of the
cofactor is bound by two cyanide ligands and a single carbon monoxide ligand.
Minimally six accessory proteins (HypAâHypF) are necessary for NiFe(CN)2CO
cofactor biosynthesis in Escherichia coli. It has been shown that the
anaerobically purified HypCâHypDâHypE scaffold complex carries the Fe(CN)2CO
moiety of this cofactor. In the present study, we have purified the HybGâHypDE
complex and used it to successfully reconstitute in vitro active Hyd from E.
coli. HybG is a homologue of HypC that is specifically required for the
maturation of Hyd-2 and also functions in the maturation of Hyd-1 of E. coli.
Maturation of active Hyd-1 and Hyd-2 could be demonstrated in extracts derived
from HybG- and HypD-deficient E. coli strains by adding anaerobically purified
HybGâHypDE complex. In vitro maturation was dependent on ATP,
carbamoylphosphate, nickel and reducing conditions. Hydrogenase maturation was
prevented when the purified HybGâHypDE complex used in the maturation assay
lacked a bound Fe(CN)2CO moiety. These findings demonstrate that it is
possible to isolate incompletely processed intermediates on the maturation
pathway and to use these to activate apo-forms of [NiFe]-hydrogenase large
subunits
Low-frequency modes in the Raman spectrum of sp-sp2 nanostructured carbon
A novel form of amorphous carbon with sp-sp2 hybridization has been recently
produced by supersonic cluster beam deposition showing the presence in the film
of both polyynic and cumulenic species [L. Ravagnan et al. Phys. Rev. Lett. 98,
216103 (2007)]. Here we present a in situ Raman characterization of the low
frequency vibrational region (400-800 cm-1) of sp-sp2 films at different
temperatures. We report the presence of two peaks at 450 cm-1 and 720 cm-1. The
lower frequency peak shows an evolution with the variation of the sp content
and it can be attributed, with the support of density functional theory (DFT)
simulations, to bending modes of sp linear structures. The peak at 720 cm-1
does not vary with the sp content and it can be attributed to a feature in the
vibrational density of states activated by the disorder of the sp2 phase.Comment: 15 pages, 5 figures, 1 tabl
Entanglement and chaos in the kicked top
The standard kicked top involves a periodically kicked angular momentum. By
considering this angular momentum as a collection of entangled spins, we
compute the bipartite entanglement dynamics as a function of the dynamics of
the classical counterpart. Our numerical results indicate that the entanglement
of the quantum top depends on the specific details of the dynamics of the
classical top rather than depending universally on the global properties of the
classical regime. These results are grounded on linking the entanglement rate
to averages involving the classical angular momentum, thereby explaining why
regular dynamics can entangle as efficiently as the classically chaotic regime.
The findings are in line with previous results obtained with a 2-particle top
model, and we show here that the standard kicked top can be obtained as a
limiting case of the 2-particle top
Expression of HIV receptors, alternate receptors and co-receptors on tonsillar epithelium: implications for HIV binding and primary oral infection
BACKGROUND: Primary HIV infection can develop from exposure to HIV in the oral cavity. In previous studies, we have documented rapid and extensive binding of HIV virions in seminal plasma to intact mucosal surfaces of the palatine tonsil and also found that virions readily penetrated beneath the tissue surfaces. As one approach to understand the molecular interactions that support HIV virion binding to human mucosal surfaces, we have examined the distribution of the primary HIV receptor CD4, the alternate HIV receptors heparan sulfate proteoglycan (HS) and galactosyl ceramide (GalCer) and the co-receptors CXCR4 and CCR5 in palatine tonsil. RESULTS: Only HS was widely expressed on the surface of stratified squamous epithelium. In contrast, HS, GalCer, CXCR4 and CCR5 were all expressed on the reticulated epithelium lining the tonsillar crypts. We have observed extensive variability, both across tissue sections from any tonsil and between tonsils, in the distribution of epithelial cells expressing either CXCR4 or CCR5 in the basal and suprabasal layers of stratified epithelium. The general expression patterns of CXCR4, CCR5 and HS were similar in palatine tonsil from children and adults (age range 3â20). We have also noted the presence of small clusters of lymphocytes, including CD4(+ )T cells within stratified epithelium and located precisely at the mucosal surfaces. CD4(+ )T cells in these locations would be immediately accessible to HIV virions. CONCLUSION: In total, the likelihood of oral HIV transmission will be determined by macro and micro tissue architecture, cell surface expression patterns of key molecules that may bind HIV and the specific properties of the infectious inoculum
A Spectroscopic Survey of Electronic Transitions of CH, CH, and CD
Electronic spectra of CH are measured in the cm
domain using cavity ring-down spectroscopy of a supersonically expanding
hydrocarbon plasma. In total, 19 (sub)bands of CH are presented, all
probing the vibrational manifold of the B electronically excited state.
The assignments are guided by electronic spectra available from matrix
isolation work, isotopic substitution experiments (yielding also spectra for
CH and CD), predictions from ab initio calculations as well as
rotational fitting and vibrational contour simulations using the available
ground state parameters as obtained from microwave experiments. Besides the
origin band, three non-degenerate stretching vibrations along the
linear backbone of the CH molecule are assigned: the mode
associated with the C-C bond vibration and the and modes
associated with CC triple bonds. For the two lowest and
bending modes, a Renner-Teller analysis is performed identifying the
() and both () and
() components. In addition, two higher lying bending
modes are observed, which are tentatively assigned as ()
and () levels. In the excitation region below the first
non-degenerate vibration (), some transitions are
observed that are assigned as even combination modes of low-lying bending
vibrations. The same holds for a transition found above the
level. From these spectroscopic data and the vibronic analysis a
comprehensive energy level diagram for the B state of CH is derived
and presented.Comment: Accepted for publication in The Journal of Physical Chemistry A (26
July 2016
Experimental evidence of thermal fluctuations on the X-ray absorption near-edge structure at the aluminum K-edge
After a review of temperature-dependent experimental x-ray absorption
near-edge structure (XANES) and related theoretical developments, we present
the Al K-edge XANES spectra of corundum and beryl for temperature ranging from
300K to 930K. These experimental results provide a first evidence of the role
of thermal fluctuation in XANES at the Al K-edge especially in the pre-edge
region. The study is carried out by polarized XANES measurements of single
crystals. For any orientation of the sample with respect to the x-ray beam, the
pre-edge peak grows and shifts to lower energy with temperature. In addition
temperature induces modifications in the position and intensities of the main
XANES features. First-principles DFT calculations are performed for both
compounds. They show that the pre-edge peak originates from forbidden 1s to 3s
transitions induced by vibrations. Three existing theoretical models are used
to take vibrations into account in the absorption cross section calculations:
i) an average of the XANES spectra over the thermal displacements of the
absorbing atom around its equilibrium position, ii) a method based on the crude
Born-Oppenheimer approximation where only the initial state is averaged over
thermal displacements, iii) a convolution of the spectra obtained for the atoms
at the equilibrium positions with an approximate phonon spectral function. The
theoretical spectra so obtained permit to qualitatively understand the origin
of the spectral modifications induced by temperature. However the correct
treatment of thermal fluctuation in XANES spectroscopy requires more
sophisticated theoretical tools
- âŠ