Modeling Coherent Anti-Stokes Raman Scattering with Time-Dependent Density Functional Theory: Vacuum and Surface Enhancement.

We present the first density functional simulations of coherent anti-Stokes Raman scattering (CARS) and an analysis of the chemical effects upon binding to a metal surface. Spectra are obtained from first-principles electronic structure calculations and are compared with available experiments and previously available theoretical results following from Hartree–Fock polarizability derivatives. A first approximation to the nonresonant portion of the CARS signal is also explored. We examine the silver pyridine cluster models of the surface chemical signal enhancement, previously introduced for surface-enhanced Raman scattering. Chemical resonant intensity enhancements of roughly 10² are found for several model clusters. The prospects of realizing further enhancement of CARS signal with metal surfaces is discussed in light of the predicted chemical enhancements

Complex Chemical Reaction Networks from Heuristics-Aided Quantum Chemistry

While structures and reactivities of many small molecules can be computed efficiently and accurately using quantum chemical methods, heuristic approaches remain essential for modeling complex structures and large-scale chemical systems. Here, we present a heuristics-aided quantum chemical methodology applicable to complex chemical reaction networks such as those arising in cell metabolism and prebiotic chemistry. Chemical heuristics offer an expedient way of traversing high-dimensional reactive potential energy surfaces and are combined here with quantum chemical structure optimizations, which yield the structures and energies of the reaction intermediates and products. Application of heuristics-aided quantum chemical methodology to the formose reaction reproduces the experimentally observed reaction products, major reaction pathways, and autocatalytic cycles

Excitonics: A Set of Gates for Molecular Exciton Processing and Signaling

Regulating energy transfer pathways through materials is a central goal of nanotechnology, as a greater degree of control is crucial for developing sensing, spectroscopy, microscopy, and computing applications. Such control necessitates a toolbox of actuation methods that can direct energy transfer based on user input. Here we introduce a proposal for a molecular exciton gate, analogous to a traditional transistor, for regulating exciton flow in chromophoric systems. The gate may be activated with an input of light or an input flow of excitons. Our proposal relies on excitation migration <i>via</i> the second excited singlet (S₂) state of the gate molecule. It exhibits the following features, only a subset of which are present in previous exciton switching schemes: picosecond time scale actuation, amplification/gain behavior, and a lack of molecular rearrangement. We demonstrate that the device can be used to produce universal binary logic or amplification of an exciton current, providing an excitonic platform with several potential uses, including signal processing for microscopy and spectroscopy methods that implement tunable exciton flux

Separation of Electromagnetic and Chemical Contributions to Surface-Enhanced Raman Spectra on Nanoengineered Plasmonic Substrates

Raman signals from molecules adsorbed on a noble metal surface are enhanced by many orders of magnitude due to the plasmon resonances of the substrate. Additionally, the enhanced spectra are modified compared to the spectra of neat molecules; many vibrational frequencies are shifted, and relative intensities undergo significant changes upon attachment to the metal. With the goal of devising an effective scheme for separating the electromagnetic and chemical effects, we explore the origin of the Raman spectra modification of benzenethiol adsorbed on nanostructured gold surfaces. The spectral modifications are attributed to the frequency dependence of the electromagnetic enhancement and to the effect of chemical binding. The latter contribution can be reproduced computationally using molecule−metal cluster models. We present evidence that the effect of chemical binding is mostly due to changes in the electronic structure of the molecule rather than to the fixed orientation of molecules relative to the substrate

Solid-State End-On to Side-On Isomerization of (NN)^2– in {[(R₂N)₃Nd]₂N₂}^2– (R = SiMe₃) Connects In Situ Ln^III(NR₂)₃/K and Isolated [Ln^II(NR₂)₃]^1– Dinitrogen Reduction

Examination of the reduction chemistry of Nd(NR2)3 (R = SiMe3) under N2 has provided connections between the in situ Ln(III)-based LnIII(NR2)3/K reductions of N2 that form side-on bound neutral (N=N)2– complexes, [(R2N)2(THF)Ln]2[μ-η2:η2-N2], and the Ln(II)-based [LnII(NR2)3]1– reductions by Sc, Gd, and Tb that form end-on bound (N=N)2– complexes, {[(R2N)3Ln]2[μ-η1:η1-N2]}2–, which are dianions. The reduction of Nd(NR2)3 by KC8 under dinitrogen in Et2O in the presence of 18-crown-6 (18-c-6) forms dark yellow solutions of [K2(18-c-6)3]{[(R2N)3Nd]2N2} at low temperatures that become green as they warm up to −35 °C in a glovebox freezer. Green crystals obtained from the solution turn yellow-brown when cooled below −100 °C, and the yellow-brown compound has an end-on Nd2(μ-η1:η1-N2) structure. The yellow-brown crystals isomerize in the solid state on the diffractometer upon warming, and at −25 °C, the crystals are green and have a side-on Nd2(μ-η2:η2-N2) structure. Collection of X-ray diffraction data at 10 °C intervals from −50 to −90 °C revealed that the isomerization occurs at temperatures below −100 °C. In the presence of tetrahydrofuran (THF), the dianionic {[(R2N)3Nd]2N2}2– system can lose an amide ligand to provide the monoanionic [(R2N)3NdIII(μ-η2:η2-N2)NdIII(NR2)2(THF)]1–, characterized by X-ray crystallography. These data suggest a connection between the in situ Ln(III)/K reductions and Ln(II) reductions that depends on solvent, temperature, the presence of a chelate, and the specific rare-earth metal

Can Mixed-Metal Surfaces Provide an Additional Enhancement to SERS?

We explore the chemical contribution to surface-enhanced Raman scattering (SERS) in mixed-metal substrates, both experimentally and by computer simulation. These substrates are composed of a chemically active, transition-metal overlayer deposited on an effective SERS substrate. We report improved analytical enhancement factors obtained by using a small surface coverage of palladium or platinum over nanostructured silver substrates. Theoretical predictions of the chemical contribution to the surface enhancement using density functional theory support the experimental results. In addition, these approaches show that the increased enhancement is due not only to an increase in surface coverage of the analyte but also to a higher Raman scattering cross section per molecule. The additional chemical enhancement in mixed-metal SERS substrates correlates with the binding energy of the analyte on the surface and includes both static and dynamical effects. SERS using mixed-metal substrates has the potential to improve sensing for a large group of analyte molecules and to aid the development of chemically specific SERS-based sensors

Introducing Ionic and/or Hydrogen Bonds into the SAM//Ga₂O₃ Top-Interface of Ag^TS/S(CH₂)_<i>n</i>T//Ga₂O₃/EGaIn Junctions

Junctions with the structure Ag^TS/S­(CH₂)_<i>n</i>T//Ga₂O₃/EGaIn (where S­(CH₂)_<i>n</i>T is a self-assembled monolayer, SAM, of n-alkanethiolate bearing a terminal functional group T) make it possible to examine the response of rates of charge transport by tunneling to changes in the strength of the interaction between T and Ga₂O₃. Introducing a series of Lewis acidic/basic functional groups (T = −OH, −SH, −CO₂H, −CONH₂, and −PO₃H) at the terminus of the SAM gave values for the tunneling current density, <i>J</i>(<i>V</i>) in A/cm², that were indistinguishable (i.e., differed by less than a factor of 3) from the values observed with n-alkanethiolates of equivalent length. The insensitivity of the rate of tunneling to changes in the terminal functional group implies that replacing weak van der Waals contact interactions with stronger hydrogen- or ionic bonds at the T//Ga₂O₃ interface does not change the shape (i.e., the height or width) of the tunneling barrier enough to affect rates of charge transport. A comparison of the injection current, <i>J</i>₀, for T = −CO₂H, and T = −CH₂CH₃−two groups having similar extended lengths (in Å, or in numbers of non-hydrogen atoms)−suggests that both groups make indistinguishable contributions to the height of the tunneling barrier