5 research outputs found
Second-Order Nonlinear Optical Responses and Concave–Convex Interactions of Size-Selective Fullerenes/Corannulene Recognition Pairs: The Effect of Fullerene Size
The
size-selective formation of eight molecular recognition pairs
between the host corannulene and fullerene guest of various size have
been studied by taking advantage of concave–convex π–π
interactions. Herein, the structures, binding interactions, electronic
absorption spectra, and first hyperpolarizabilities have been explored
using density functional theory calculations. It is found that with
the aim to maximize the concave–convex shape complementarity,
the base of fullerene can be modified at certain angles with the central
ring plane of C<sub>20</sub>H<sub>10</sub> (0° for complexes <b>1</b>–<b>4</b> and 46°, 34°, 19°,
and 5° for complexes <b>5</b>–<b>8</b>, respectively).
The interaction energies depend linearly on the convex surface area
and the size of the fullerene sphere. Further, the results of first
hyperpolarizabilities show that the shape of the fullerene is the
dominant factor for complexes <b>1</b>–<b>4</b> because of the intramolecular charge transfer (CT) within fullerene
cage. Among them, complex <b>4</b> presents the largest β<sub>tot</sub> value as 5.64 × 10<sup>–30</sup> esu because
of the more obvious intramolecular CT from the upper part to the bottom
part of the C<sub>70</sub> cage, derived from the larger height of
the cage. On the other hand, low-lying CT character accounts for a
large part of the first hyperpolarizability. The achieved understanding
provides the prospect of size-selective strategy for enhancing the
concave–convex interaction and second order nonlinear optical
response in the recognition of fullerenes
Third-Order Nonlinear Optical Properties of Endohedral Fullerene (H<sub>2</sub>)<sub>2</sub>@C<sub>70</sub> and (H<sub>2</sub>O)<sub>2</sub>@C<sub>70</sub> Accompanied by the Prospective of Novel (HF)<sub>2</sub>@C<sub>70</sub>
In view of the experimental
observation of (H<sub>2</sub>)<sub>2</sub>@C<sub>70</sub> and (H<sub>2</sub>O)<sub>2</sub>@C<sub>70</sub>, it has been suggested that
hydrogen fluoride (HF) dimer can be
completely localized within the sub-nanospace inside the fullerene
C<sub>70</sub> cage. With the aim of quantum chemical prospective
of (HF)<sub>2</sub>@C<sub>70</sub>, electronic structure calculations
of C<sub>60</sub> hosting H<sub>2</sub>, HF, and H<sub>2</sub>O monomers,
as well as C<sub>70</sub> hosting H<sub>2</sub>, HF, and H<sub>2</sub>O monomers and dimers, were performed by using the density functional
theory, together with the quantum theory of atoms in molecules, the
natural population, and interaction energy calculation. The F–H···F
bonding energy inside C<sub>70</sub> was estimated at −13.25
kcal/mol, which is smaller than that of free dimer in the gas phase
(−8.37 kcal/mol). Exploration of various featured properties
suggests that (HF)<sub>2</sub>@C<sub>70</sub> may be also regarded
as a unique system composed of both inter- and intramolecular interactions
like (H<sub>2</sub>)<sub>2</sub>@C<sub>70</sub> and (H<sub>2</sub>O)<sub>2</sub>@C<sub>70</sub>. In addition, absorption spectroscopy
and linear and nonlinear optical coefficients of C<sub>60</sub> hosting
H<sub>2</sub>, HF, and H<sub>2</sub>O monomers, as well as C<sub>70</sub> hosting H<sub>2</sub>, HF, and H<sub>2</sub>O monomers and dimers,
have also been forecasted. The results show that there is almost no
influence of embedded H<sub>2</sub>, HF, and H<sub>2</sub>O monomers
and dimers on the peak wavelength of absorption spectra for C<sub>60</sub> and C<sub>70</sub>. Endohedral C<sub>70</sub> possesses
the larger second hyperpolarizabilities with respect to that of endohedral
C<sub>60</sub>, indicating that the effect of cage size is effective
in the second hyperpolarizabilities of endohedral fullerenes. The
study will benefit not only the designation and the syntheses of the
novel molecular (HF)<sub>2</sub>@C<sub>70</sub> but also the understanding
of the structures and properties of endohedral fullerenes
Self-Assembled Donor–Acceptor Chromophores: Evident Layer Effect on the First Hyperpolarizability and Two-Dimensional Charge Transfer Character
Self-assembled
donor–acceptor chromophores have extensive
applications in photofunctional devices owing to their unique charge
transport properties. To explore the possibility of improving nonlinear
optical (NLO) properties by self-assembly to multilayer complexes,
we theoretically investigated the geometric and electronic structures,
interlayer weak interactions, absorption spectra, charge transfer
properties, polarizabilities (α), and first hyperpolarizabilities
(β) of naphthalimide, -phenyl, and -naphthyl monomers, dimers,
and trimers by increasing the layer number <i>n</i> (<i>n</i> = 1, 2, 3). Different stacking patterns of their dimers
were also taken into account. These show that parallel stacking patterns
are conducive to maximizing overlap with respect to antiparallel ones
due to the concept of optimal π-orbital overlap is more vast
than purely maximizing cofacial overlap to improve charge transport.
The decreases in band gap for the di/trimeric versus monomeric naphthalimide,
-phenyl, and -naphthyl monomers indicate the possibility of more favorable
photoinduced electron transition in the aggregate when compared to
the monomer. The linear and second-order NLO properties of these complexes
are investigated in detail. The α values increase linearly as
the increased number <i>n</i> of the layer (<i>n</i> = 1, 2, and 3), providing a new kind of tendency forecast method
for the linear optical properties. Along with the increasing electron
donating ability of the donor, the β<sub>tot</sub> values of
monomers increased, revealing the general rule of designing NLO molecular
materials. The dependence of β<sub>tot</sub> value on the layer
number shows that the β<sub>tot</sub> value increased with the
increased number of layer, which can be rationalized by considering
the enhancement of interlayer electronic transition and two-dimensional
NLO character with the two charge transfer axes. We hope this work
may evoke one’s attention to design new, highly efficient second-order
NLO materials with excellent building blocks: multilayer complexes
Nanoscale Polysulfides Reactors Achieved by Chemical Au–S Interaction: Improving the Performance of Li–S Batteries on the Electrode Level
In this work, the chemical interaction
of cathode and lithium polysulfides
(LiPSs), which is a more targeted approach for completely preventing
the shuttle of LiPSs in lithium–sulfur (Li–S) batteries,
has been established on the electrode level. Through simply posttreating
the ordinary sulfur cathode in atmospheric environment just for several
minutes, the Au nanoparticles (Au NPs) were well-decorated on/in the
surface and pores of the electrode composed of commercial acetylene
black (CB) and sulfur powder. The Au NPs can covalently stabilize
the sulfur/LiPSs, which is advantageous for restricting the shuttle
effect. Moreover, the LiPSs reservoirs of Au NPs with high conductivity
can significantly control the deposition of the trapped LiPSs, contributing
to the uniform distribution of sulfur species upon charging/discharging.
The slight modification of the cathode with <3 wt % Au NPs has
favorably prospered the cycle capacity and stability of Li–S
batteries. Moreover, this cathode exhibited an excellent anti-self-discharge
ability. The slight decoration for the ordinary electrode, which can
be easily accessed in the industrial process, provides a facile strategy
for improving the performance of commercial carbon-based Li–S
batteries toward practical application
Second-Order Nonlinear Optical Properties of Carboranylated Square-Planar Pt(II) Zwitterionic Complexes: One-/Two-Dimensional Difference and Substituent Effect
Zwitterionic
complexes have been the subject of great interest
in the past several decades due to their multifunctional application
in supramolecular chemistry. Herein, a series of internally stable
charge-compensated carboranylated square-planar PtÂ(II) zwitterionic
complexes have been explored by density functional theory aim to assessing
their structures, the first hyperpolarizabilities, first hyperpolarizability
densities, and electronic absorption spectra. It is found that the
first hyperpolarizabilities of two-dimensional (2D) structure complexes
are much larger with respect to the one-dimensional complex. It is
ascribed to the lower transition energy and more obvious charge transfer,
which can be further illustrated by their large amplitude and separate
distribution of first hyperpolarizability density. In addition, the
first hyperpolarizabilities of 2D complexes can be further significantly
modified by introducing electron-donating/withdrawing groups on the
carborane cage. As a consequence, we believe that these 2D zwitterionic
complexes can behave as novel second-order nonlinear optical chromophore
with a promising future