23 research outputs found
Model ab initio study of charge carrier solvation and large polaron formation on conjugated carbon chains
Using long C_{N}H_{2} conjugated carbon chains with the polyynic structure as
prototypical examples of one-dimensional (1D) semiconductors, we discuss
self-localization of excess charge carriers into 1D large polarons in the
presence of the interaction with a surrounding polar solvent. The solvation
mechanism of self-trapping is different from the polaron formation due to
coupling with bond-length modulations of the underlying atomic lattice
well-known in conjugated polymers. Model ab initio computations employing the
hybrid B3LYP density functional in conjunction with the polarizable continuum
model are carried out demonstrating the formation of both electron- and
hole-polarons. Polarons can emerge entirely due to solvation but even larger
degrees of charge localization occur when accompanied by atomic displacements
Energy transfer from colloidal nanocrystals into Si substrates studied via photoluminescence photon counts and decay kinetics
We use time-resolved photoluminescence (PL) kinetics and PL intensity measurements to study the decay of photoexcitations in colloidal CdSe/ZnS nanocrystals grafted on SiO 2 − Si substrates with a wide range of the SiO 2 spacer layer thicknesses. The salient features of experimental observations are found to be in good agreement with theoretical expectations within the framework of modification of spontaneous decay of electric-dipole excitons by their environment. Analysis of the experimental data reveals that energy transfer (ET) from nanocrystals into Si is a major enabler of substantial variations in decay rates, where we quantitatively distinguish contributions from nonradiative and radiative ET channels. We demonstrate that time-resolved PL kinetics provides a more direct assessment of ET, while PL intensity measurements are also affected by the specifics of the generation and emission processes
Charge carrier solvation and large polaron formation on a polymer chain revealed in model ab initio computations
When an excess charge carrier is added to a semiconducting polymer chain, it
is well known that the carrier may self-trap into a polaronic state accompanied
by a bond length adjustment pattern. A different mechanism of self-localization
is the solvation of charge carriers expected to take place when the polymer
chain is immersed in polar media such as common solvents. We use
state-of-the-art ab initio computations in conjunction with the Polarizable
Continuum Model to unequivocally demonstrate solvation-induced self-consistent
charge localization into large-radius one-dimensional (1D) polarons on long
carbon chains with the polyynic structure. Within the framework
used, the solvation results in a much more pronounced charge localization. We
believe this mechanism of polaron formation to be of relevance for various 1D
semiconductors in polar environments
A theoretical investigation of the low lying electronic structure of poly(p-phenylene vinylene)
The two-state molecular orbital model of the one-dimensional phenyl-based
semiconductors is applied to poly(p-phenylene vinylene). The energies of the
low-lying excited states are calculated using the density matrix
renormalization group method. Calculations of both the exciton size and the
charge gap show that there are both Bu and Ag excitonic levels below the band
threshold. The energy of the 1Bu exciton extrapolates to 2.60 eV in the limit
of infinite polymers, while the energy of the 2Ag exciton extrapolates to 2.94
eV. The calculated binding energy of the 1Bu exciton is 0.9 eV for a 13
phenylene unit chain and 0.6 eV for an infinite polymer. This is expected to
decrease due to solvation effects. The lowest triplet state is calculated to be
at ca. 1.6 eV, with the triplet-triplet gap being ca. 1.6 eV. A comparison
between theory, and two-photon absorption and electroabsorption is made,
leading to a consistent picture of the essential states responsible for most of
the third-order nonlinear optical properties. An interpretation of the
experimental nonlinear optical spectroscopies suggests an energy difference of
ca. 0.4 eV between the vertical energy and ca. 0.8 eV between the relaxed
energy, of the 1Bu exciton and the band gap, respectively.Comment: LaTeX, 19 pages, 7 eps figures included using epsf. To appear in
Physical Review B, 199
Polaron formation for a non-local electron-phonon coupling: A variational wave-function study
We introduce a variational wave-function to study the polaron formation when
the electronic transfer integral depends on the relative displacement between
nearest-neighbor sites giving rise to a non-local electron-phonon coupling with
optical phonon modes. We analyze the ground state properties such as the
energy, the electron-lattice correlation function, the phonon number and the
spectral weight. Variational results are found in good agreement with analytic
weak-coupling perturbative calculations and exact numerical diagonalization of
small clusters. We determine the polaronic phase diagram and we find that the
tendency towards strong localization is hindered from the pathological sign
change of the effective next-nearest-neighbor hopping.Comment: 11 page