11,472 research outputs found
Optical absorption in small BN and C nanotubes
We present a theoretical study of the optical absorption spectrum of small
boron-nitride and carbon nanotubes using time-dependent density-functional
theory and the random phase approximation. Both for C and BN tubes, the
absorption of light polarized perpendicular to the tube-axis is strongly
suppressed due to local field effects. Since BN-tubes are wide band-gap
insulators, they only absorb in the ultra-violet energy regime, independently
of chirality and diameter. In comparison with the spectra of the single C and
BN-sheets, the tubes display additional fine-structure which stems from the
(quasi-) one-dimensionality of the tubes and sensitively depends on the
chirality and tube diameter. This fine structure can provide additional
information for the assignment of tube indices in high resolution optical
absorption spectroscopy.Comment: 5 pages, 3 figure
Effect of many modes on self-polarization and photochemical suppression in cavities
The standard description of cavity-modified molecular reactions typically involves a single (resonant) mode, while in reality, the quantum cavity supports a range of photon modes. Here, we demonstrate that as more photon modes are accounted for, physicochemical phenomena can dramatically change, as illustrated by the cavity-induced suppression of the important and ubiquitous process of proton-coupled electron-transfer. Using a multi-trajectory Ehrenfest treatment for the photon-modes, we find that self-polarization effects become essential, and we introduce the concept of self-polarization-modified Born–Oppenheimer surfaces as a new construct to analyze dynamics. As the number of cavity photon modes increases, the increasing deviation of these surfaces from the cavity-free Born–Oppenheimer surfaces, together with the interplay between photon emission and absorption inside the widening bands of these surfaces, leads to enhanced suppression. The present findings are general and will have implications for the description and control of cavity-driven physical processes of molecules, nanostructures, and solids embedded in cavities
Time and energy-resolved two photon-photoemission of the Cu(100) and Cu(111) metal surfaces
We present calculations on energy- and time-resolved two-photon photoemission
spectra of images states in Cu(100) and Cu(111) surfaces. The surface is
modeled by a 1D effective potential and the states are propagated within a
real-space, real-time method. To obtain the energy resolved spectra we employ a
geometrical approach based on a subdivision of space into two regions. We treat
electronic inelastic effects by taking into account the scattering rates
calculated within a GW scheme. To get further insight into the decaying
mechanism we have also studied the effect of the variation of the classical
Hartree potential during the excitation. This effect turns out to be small.Comment: 11 pages, 7 figure
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Universal slow plasmons and giant field enhancement in atomically thin quasi-two-dimensional metals
Plasmons depend strongly on dimensionality: while plasmons in three-dimensional systems start with finite energy at wavevector q = 0, plasmons in traditional two-dimensional (2D) electron gas disperse as ωp∼q√. However, besides graphene, plasmons in real, atomically thin quasi-2D materials were heretofore not well understood. Here we show that the plasmons in real quasi-2D metals are qualitatively different, being virtually dispersionless for wavevectors of typical experimental interest. This stems from a broken continuous translational symmetry which leads to interband screening; so, dispersionless plasmons are a universal intrinsic phenomenon in quasi-2D metals. Moreover, our ab initio calculations reveal that plasmons of monolayer metallic transition metal dichalcogenides are tunable, long lived, able to sustain field intensity enhancement exceeding 107, and localizable in real space (within ~20 nm) with little spreading over practical measurement time. This opens the possibility of tracking plasmon wave packets in real time for novel imaging techniques in atomically thin materials
A TDDFT study of the excited states of DNA bases and their assemblies
We present a detailed study of the optical absorption spectra of DNA bases
and base pairs, carried out by means of time dependent density functional
theory. The spectra for the isolated bases are compared to available
theoretical and experimental data and used to assess the accuracy of the method
and the quality of the exchange-correlation functional: Our approach turns out
to be a reliable tool to describe the response of the nucleobases. Furthermore,
we analyze in detail the impact of hydrogen bonding and -stacking in the
calculated spectra for both Watson-Crick base pairs and Watson-Crick stacked
assemblies. We show that the reduction of the UV absorption intensity
(hypochromicity) for light polarized along the base-pair plane depends strongly
on the type of interaction. For light polarized perpendicular to the basal
plane, the hypochromicity effect is reduced, but another characteristic is
found, namely a blue shift of the optical spectrum of the base-assembly
compared to that of the isolated bases. The use of optical tools as
fingerprints for the characterization of the structure (and type of
interaction) is extensively discussed.Comment: 31 pages, 8 figure
Tailoring electronic and optical properties of TiO2: nanostructuring, doping and molecular-oxide interactions
Titanium dioxide is one of the most widely investigated oxides. This is due
to its broad range of applications, from catalysis to photocatalysis to
photovoltaics. Despite this large interest, many of its bulk properties have
been sparsely investigated using either experimental techniques or ab initio
theory. Further, some of TiO2's most important properties, such as its
electronic band gap, the localized character of excitons, and the localized
nature of states induced by oxygen vacancies, are still under debate. We
present a unified description of the properties of rutile and anatase phases,
obtained from ab initio state of the art methods, ranging from density
functional theory (DFT) to many body perturbation theory (MBPT) derived
techniques. In so doing, we show how advanced computational techniques can be
used to quantitatively describe the structural, electronic, and optical
properties of TiO2 nanostructures, an area of fundamental importance in applied
research. Indeed, we address one of the main challenges to TiO2-photocatalysis,
namely band gap narrowing, by showing how to combine nanostructural changes
with doping. With this aim we compare TiO2's electronic properties for 0D
clusters, 1D nanorods, 2D layers, and 3D bulks using different approximations
within DFT and MBPT calculations. While quantum confinement effects lead to a
widening of the energy gap, it has been shown that substitutional doping with
boron or nitrogen gives rise to (meta-)stable structures and the introduction
of dopant and mid-gap states which effectively reduce the band gap. Finally, we
report how ab initio methods can be applied to understand the important role of
TiO2 as electron-acceptor in dye-sensitized solar cells. This task is made more
difficult by the hybrid organic-oxide structure of the involved systems.Comment: 32 pages, 8 figure
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