Remote controlled optical manipulation of bimetallic nanoparticle catalysts using peptides
Explore the source record for details and available documents.
99 GENERAL AND MISCELLANEOUS↗
SEARCH · Engineering Papers
Results for “CIS”
Search indexed NASA NTRS and DOE OSTI research on propulsion, heat transfer, battery materials and energy systems. Follow report and document links to the original sources.
Quote a phrase for an exact phrase match. Source license links do not imply unrestricted reuse.
On the choice of reference orbitals for linear-response calculations of solution-phase K-edge X-ray absorption spectra
The simplest response theory methods for computing vertical excitation spectra in condensed-phase are configuration interaction with single excitations (CIS) and linear-response time-dependent density functional theory (TDDFT) within the Tamm–Dancoff approximation. In applications to X-ray absorption spectroscopy (XAS), methods like CIS and TDDFT that codify only single excitations into the wave function are prone to catastrophic errors in main-edge and post-edge features whose shapes act as a crucial fingerprint in structural analyses of liquids. Here, we show that these errors manifest primarily due to a lack of orbital relaxation in conventional linear-response theories and that core-ionized (n - 1-electron) references, like those of electron-affinity TDDFT, can eliminate the errors in the spectral profile, even in the highest-energy parts of the post-edge. Crucially, we find that single excitations atop core-ionized references are sufficient to elucidate liquid-phase XAS spectra with semi-quantitative accuracy, opening the door for methods like electron-affinity CIS/TDDFT to be used as efficient alternatives to higher-order wave function approaches.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Stereogenic-at-silicon hybrid conjugated polymers
Stereoregularity in carbon-based polymers impacts critical physical properties such as crystallinity, but achieving comparable precision in polysilanes remains challenging. Herein, we report the synthesis of hybrid σ,π-conjugated polysilanes with defined stereoregularity, derived from cis- and trans-cyclosilane building blocks. Using Kumada polycondensation, we accessed a series of atactic, trans-enriched, and cis-enriched polysilanes, enabling a systematic investigation of how tacticity influences thermal and optical properties. Differential scanning calorimetry revealed distinct glass transition behaviors for stereoregular polymers compared to their atactic counterpart, and UV-vis spectroscopy demonstrated enhanced spectral resolution upon annealing of stereoregular films. A linear silane-based analog further underscored the structural impact of cyclic stereogenic units. These findings highlight how stereochemical precision in silicon-containing backbones can modulate macromolecular properties, opening avenues for the rational design of stereoregular polysilanes.
36 MATERIALS SCIENCE↗
Infrared absorption of 3-propenonyl (⋅CH{sub 2}CHCO) radical generated upon photolysis of acryloyl chloride [CH{sub 2}CHC(O)Cl] in solid para-H{sub 2}
Irradiation at 193 nm of a p-H{sub 2} matrix containing acryloyl chloride CH{sub 2}CHC(O)Cl at 3.2 K yielded infrared absorption lines at 3143.6 (ν{sub 1}), 3057.0 (ν{sub 2}), 3048.0 (ν{sub 3}), 2103.1 (ν{sub 4}), 1461.0 (ν{sub 5}), 1349.8 (ν{sub 6}), 1223.7 (ν{sub 11}+ν{sub 12} or 2ν{sub 12}), 1092.8 (ν{sub 8}), 918.1 (ν{sub 9}), 691.0 (ν{sub 10}), 624.3 (ν{sub 11}), and 597.1 (ν{sub 12}) cm{sup −1} that are assigned to the 3-propenonyl (⋅CH{sub 2}CHCO) radical. The assignments are based on the photolytic behavior and a comparison of observed vibrational wavenumbers and infrared intensities with those predicted with the B3PW91/aug-cc-pVDZ method. The observation is consistent with a major radical formation channel CH{sub 2}CHCO + Cl followed by escape of the Cl atom from the original p-H{sub 2} cage. The observation of 3-propenonyl (⋅CH{sub 2}CHCO) radical but not 3-propenalyl (s-cis- or s-trans-CH{sub 2}CHĊO) radical indicates that the former is the most stable isomer and that the barrier heights for conversion from s-cis- or s-trans-CH{sub 2}CHĊO to ⋅CH{sub 2}CHCO are small.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Approximate photochemical dynamics of azobenzene with reactive force fields
We have fitted reactive force fields of the ReaxFF type to the ground and first excited electronic states of azobenzene, using global parameter optimization by genetic algorithms. Upon coupling with a simple energy-gap transition probability model, this setup allows for completely force-field-based simulations of photochemical cis→trans- and trans→cis-isomerizations of azobenzene, with qualitatively acceptable quantum yields. This paves the way towards large-scale dynamics simulations of molecular machines, including bond breaking and formation (via the reactive force field) as well as photochemical engines (presented in this work)
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Ultrafast carrier dynamics in CuInS{sub 2} quantum dots
The ultrafast carrier dynamics in CuInS{sub 2} (CIS) quantum dots (QDs) was studied by means of femtosecond transient absorption (TA) spectroscopy. The size-dependent 1S transition energy determined from bleaching spectra is in agreement with that calculated on the finite-depth-well model in the effective mass approximation. The TA bleaching comes from filling of electron quantized levels, allowing us to know the dynamics of the 1S electron in CIS QDs. The sub-100-ps electron trapping at surface defects in bare QDs accelerates with decreasing QD size, while is effectively suppressed in well-passivated CIS/ZnS core/shell QDs.
36 MATERIALS SCIENCE↗
The atomic structure, band gap, and electrostatic potential at the (112)[11{sup ¯}0] twin grain boundary of CuInSe{sub 2}
To develop a higher efficiency thin-film compound photovoltaic (PV) cell, it is crucial to understand not only the key factors determining the stability of the grain boundary (GB) but also the band gap and band bending at the GB in the photoabsorption layer. In this study, we investigate the atomic structure, band gap, and electrostatic potential at the (112)[11{sup ¯}0] twin GB of CuInSe{sub 2} (CIS), which is typically used in the photoabsorption layer in thin-film compound PV cells. We utilize aberration-corrected scanning transmission electron microscopy and first-principles hybrid-functional calculations. We find that the formation energies of the twin GB in CIS are very small: 0.03–0.15 J/m{sup 2}. The local coordination of the Se at the GB is a primary factor modulating the GB energy, band gap, and the electrostatic potential at the GB.
36 MATERIALS SCIENCE↗
Conformational effect of dicyclo-hexano-18-crown-6 on isotopic fractionation of zinc: DFT approach
Generalized gradient approximated BP86 density functional employing triple zeta valence plus polarization (TZVP) basis set has been used to compute the reduced partition function ratio and isotopic separation factor for zinc isotopes. The isotopic separation factor was found to be in good agreement with the experimental results. The isotopic separation factor was found to depend on the conformation of the crown ether ligand. The trans-trans conformation shows the highest fractionation compared to cis-cis conformer. The present theoretical results can thus be used to plan the isotope separation experiments.
36 MATERIALS SCIENCE↗
Photochemistry of glycolaldehyde in cryogenic matrices
The photochemistry of glycolaldehyde (GA) upon irradiation at 266 nm is investigated in argon, nitrogen, neon, and para-hydrogen matrices by IR spectroscopy. Isomerization and fragmentation processes are found to compete. The hydrogen-bonded Cis-Cis form of GA is transformed mainly to the open Trans-Trans conformer and to CO and CH{sub 3}OH fragments and their mixed complexes. Different photo-induced behaviours appear depending on the matrix. In nitrogen, small amounts of Trans-Gauche and Trans-Trans conformers are detected after deposition and grow together upon irradiation. The Trans-Gauche conformer is characterized for the first time. In para-hydrogen due to a weaker cage effect additional H{sub 2}CO and HCO fragments are seen. Calculations of the potential energy surfaces of S{sub 0}, S{sub 1}, and T{sub 1} states – to analyse the torsional deformations which are involved in the isomerization process – and a kinetic analysis are presented to investigate the different relaxation pathways of GA. Fragmentation of GA under UV irradiation through the CO+CH{sub 3}OH molecular channel is a minor process, as in the gas phase.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Charge carrier transport and collection enhancement of copper indium diselenide photoactive nanoparticle-ink by laser crystallization
There has been increasing needs for cost-effective and high performance thin film deposition techniques for photovoltaics. Among all deposition techniques, roll-to-roll printing of nanomaterials has been a promising method. However, the printed thin film contains many internal imperfections, which reduce the charge-collection performance. Here, direct pulse laser crystallization (DPLC) of photoactive nanoparticles-inks is studied to meet this challenge. In this study, copper indium selenite (CIS) nanoparticle-inks is applied as an example. Enhanced crystallinity, densified structure in the thin film is resulted after DLPC under optimal conditions. It is found that the decreased film internal imperfections after DPLC results in reducing scattering and multi-trapping effects. Both of them contribute to better charge-collection performance of CIS absorber material by increasing extended state mobility and carrier lifetime, when carrier transport and kinetics are coupled. Charge carrier transport was characterized after DPLC, showing mobility increased by 2 orders of magnitude. Photocurrent under AM1.5 illumination was measured and shown 10 times enhancement of integrated power density after DPLC, which may lead to higher efficiency in photo-electric energy conversion.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Conical intersections and diabatic potential energy surfaces for the three lowest electronic singlet states of H{sub 3}{sup +}
We calculate the adiabatic Potential Energy Surfaces (PESs) and the Non-Adiabatic Coupling Terms (NACTs) for the three lowest singlet states of H{sub 3}{sup +} in hyperspherical coordinates as functions of hyperangles (θ and ϕ) for a grid of fixed values of hyperradius (1.5 ⩽ ρ ⩽ 20 bohrs) using the MRCI level of methodology employing ab initio quantum chemistry package (MOLPRO). The NACT between the ground and the first excited state translates along the seams on the θ − ϕ space, i.e., there are six Conical Intersections (CIs) at each θ (60° ⩽ θ ⩽ 90°) within the domain, 0 ⩽ ϕ ⩽ 2π. While transforming the adiabatic PESs to the diabatic ones, such surfaces show up six crossings along those seams. Our beyond Born-Oppenheimer approach could incorporate the effect of NACTs accurately and construct single-valued, continuous, smooth, and symmetric diabatic PESs. Since the location of CIs and the spatial amplitudes of NACTs are most prominent around ρ = 10 bohrs, generally only those results are depicted.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Tuning the optical emission of MoS{sub 2} nanosheets using proximal photoswitchable azobenzene molecules
We report photoluminescence measurements performed on monolayer- and two-layer-MoS{sub 2} placed on two types of mixed self-assembled monolayers (mSAMs) of photoswitchable azobenzene molecules. The two mSAMs differ via the electronegative character of the azobenzene derivatives. Thin layers of a transition metal dichalcogenide—MoS{sub 2}—were mechanically exfoliated on mSAM to allow for direct interaction between the molecules and the MoS{sub 2} layers. When the MoS{sub 2} nanosheet is in contact with the electropositive azobenzene molecules in trans configuration, an emission side band at lower energies and at low excitation powers suggest n-type doping. The photoisomerization of the molecules from trans to cis configuration lowers the doping, quenching the side band and enhancing the overall PL efficiency by a factor of ∼3. Opposite results were observed with the chlorinated, more electronegative molecules, exhibiting a reversed trend in the PL efficiency between trans and cis, but with an overall larger intensity. The type of doping induced by the two types of mSAMs was determined by Kelvin probe force microscopy technique.
75 CONDENSED MATTER PHYSICS, SUPERCONDUCTIVITY AND↗
Vibrational predissociation and vibrationally induced isomerization of 3-aminophenol-ammonia
We investigate the vibrational predissociation dynamics of the hydrogen-bonded 3-aminophenol-ammonia cluster (3-AP-NH{sub 3}) in the OH and NH stretching regions. Vibrational excitation provides enough energy to dissociate the cluster into its constituent 3-AP and NH{sub 3} monomers, and we detect the 3-AP fragments via (1 + 1) resonance-enhanced multiphoton ionization (REMPI). The distribution of vibrational states of the 3-AP fragment suggests the presence of two distinct dissociation pathways. The first dissociation channel produces a broad, unstructured feature in the REMPI-action spectrum after excitation of any of the OH or NH stretching vibrations, pointing to a nearly statistical dissociation pathway with extensive coupling among the vibrations in the cluster during the vibrational predissociation. The second dissociation channel produces distinct, resolved features on top of the broad feature but only following excitation of the OH or symmetric NH{sub 3} stretch in the cluster. This striking mode-specificity is consistent with strong coupling of these two modes to the dissociation coordinate (the O–H⋯N bond). The presence of clearly resolved transitions to the electronic origin and to the 10a{sup 2} + 10b{sup 2} state of the cis-3-AP isomer shows that vibrational excitation is driving the isomerization of the trans-3-AP-NH{sub 3} isomer to the cis-3-AP-NH{sub 3} isomer in the course of the dissociation.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
A general ansatz for constructing quasi-diabatic states in electronically excited aggregated systems
We present a general method for analyzing the character of singly excited states in terms of charge transfer (CT) and locally excited (LE) configurations. The analysis is formulated for configuration interaction singles (CIS) singly excited wave functions of aggregate systems. It also approximately works for the second-order approximate coupled cluster singles and doubles and the second-order algebraic-diagrammatic construction methods [CC2 and ADC(2)]. The analysis method not only generates a weight of each character for an excited state, but also allows to define the related quasi-diabatic states and corresponding coupling matrix elements. In the character analysis approach, we divide the target system into domains and use a modified Pipek-Mezey algorithm to localize the canonical MOs on each domain, respectively. The CIS wavefunction is then transformed into the localized basis, which allows us to partition the wavefunction into LE configurations within domains and CT configuration between pairs of different domains. Quasi-diabatic states are then obtained by mixing excited states subject to the condition of maximizing the weight of one single LE or CT configuration (localization in configuration space). Different aims of such a procedure are discussed, either the construction of pure LE and CT states for analysis purposes (by including a large number of excited states) or the construction of effective models for dynamics calculations (by including a restricted number of excited states). Applications are given to LE/CT mixing in π-stacked systems, charge-recombination matrix elements in a hetero-dimer, and excitonic couplings in multi-chromophoric systems.
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSIC↗
Ground and excited state properties of high performance anthocyanidin dyes-sensitized solar cells in the basic solutions
The aglycones of anthocyanidin dyes were previously reported to form carbinol pseudobase, cis-chalcone, and trans-chalcone due to the basic levels. The further investigations of ground and excited state properties of the dyes were characterized using density functional theory with PCM(UFF)/B3LYP/6-31+G(d,p) level in the basic solutions. However, to the best of our knowledge, the theoretical investigation of their potential photosensitizers has never been reported before. In this paper, the theoretical photovoltaic properties sensitized by dyes have been successfully investigated including the electron injections, the ground and excited state oxidation potentials, the estimated open circuit voltages, and the light harvesting efficiencies. The results prove that the electronic properties represented by dyes’ LUMO-HOMO levels will affect to the photovoltaic performances. Cis-chalcone dye is the best anthocyanidin aglycone dye with the electron injection spontaneity of −1.208 eV, the theoretical open circuit voltage of 1.781 V, and light harvesting efficiency of 56.55% due to the best HOMO-LUMO levels. Moreover, the ethanol solvent slightly contributes to the better cell performance than the water solvent dye because of the better oxidation potential stabilization in the ground state as well as in the excited state. These results are in good agreement with the known experimental report that the aglycones of anthocyanidin dyes in basic solvent are the high potential photosensitizers for dye-sensitized solar cell.
74 ATOMIC AND MOLECULAR PHYSICS↗
Spin-flip, tensor equation-of-motion configuration interaction with a density-functional correction: A spin-complete method for exploring excited-state potential energy surfaces
We revisit the formalism of the spin-adapted, spin-flip (SA-SF) configuration-interaction singles (CIS) method based on a tensor equation-of-motion formalism that affords proper spin eigenstates without sacrificing single-reference simplicity. Matrix elements for SA-SF-CIS are then modified in a manner similar to collinear spin-flip time-dependent density functional theory (SF-TDDFT), to include a DFT exchange-correlation correction. The performance of this method, which we call SA-SF-DFT, is evaluated numerically and we find that it systematically improves the energies of electronic states that exhibit significant spin contamination within the conventional SF-TDDFT approach. The new method cures the state assignment problem that plagues geometry optimizations and ab initio molecular dynamics simulations using traditional SF-TDDFT, without sacrificing computational efficiency, and furthermore provides correct topology at conical intersections, including those that involve the ground state, unlike conventional TDDFT. As such, SA-SF-DFT appears to be a promising method for generating excited-state potential energy surfaces at DFT cost.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Communication: Analytical optimal pulse shapes obtained with the aid of genetic algorithms: Controlling the photoisomerization yield of retinal
We recently proposed a Quantum Optimal Control (QOC) method constrained to build pulses from analytical pulse shapes [R. D. Guerrero et al., J. Chem. Phys. 143(12), 124108 (2015)]. This approach was applied to control the dissociation channel yields of the diatomic molecule KH, considering three potential energy curves and one degree of freedom. In this work, we utilized this methodology to study the strong field control of the cis-trans photoisomerization of 11-cis retinal. This more complex system was modeled with a Hamiltonian comprising two potential energy surfaces and two degrees of freedom. The resulting optimal pulse, made of 6 linearly chirped pulses, was capable of controlling the population of the trans isomer on the ground electronic surface for nearly 200 fs. The simplicity of the pulse generated with our QOC approach offers two clear advantages: a direct analysis of the sequence of events occurring during the driven dynamics, and its reproducibility in the laboratory with current laser technologies.
37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CH↗
Platinum (II) azatetrabenzoporphyrins for near-infrared organic light emitting diodes
In this paper, we describe a series of platinum (II) azatetrabenzoporphyrin emitters for near-infrared (NIR) organic light emitting diode (OLED) applications. Platinum (II) aza-triphenyltetrabenzoporphyrin (PtNTBP) results in a 72 nm shift in the photoluminescent (PL) emission spectrum to 842nm compared to 770nm of the platinum (II) tetraphenyltetrabenzoporphyrin (PtTPTBP). Also, the full width at half maximum of the emission spectrum of PtNTBP was significantly narrowed to 27 nm compared to 40nm for PtTPTBP. The multilayer devices fabricated by thermal vacuum evaporation process employing PtTPTBP, PtNTBP, and cis-PtN 2 TBP exhibit electroluminescent (EL) emission peak at 770 nm, 848 nm, and 846 nm with the peak external quantum efficiency (EQE) of 8.0%, 2.8%, and 1.5%, respectively. Even with the decrease in EQE of devices employing PtNTBP and cis-PtN 2 TBP compared with those employing PtTPTBP, the combination of the spectral narrowing and the bathochromic shift to lower energy EL emission demonstrates the promise of PtNTBP for NIR applications. In the meanwhile, the solution-processed single-layer device using PtNTBP demonstrates the EQE of 0.33% and the peak EL emission at 844 nm.
36 MATERIALS SCIENCE↗