Validation of the CoGEF Method as a Predictive Tool for Polymer Mechanochemistry

The development of force-responsive molecules called mechanophores is a central component of the field of polymer mechanochemistry. Mechanophores enable the design and fabrication of polymers for a variety of applications ranging from sensing to molecular release and self-healing materials. Nevertheless, an insufficient understanding of structure–activity relationships limits experimental development, and thus computation is necessary to guide the structural design of mechanophores. The constrained geometries simulate external force (CoGEF) method is a highly accessible and straightforward computational technique that simulates the effect of mechanical force on a molecule and enables the prediction of mechanochemical reactivity. Here, we use the CoGEF method to systematically evaluate every covalent mechanophore reported to date and compare the predicted mechanochemical reactivity to experimental results. Molecules that are mechanochemically inactive are also studied as negative controls. In general, mechanochemical reactions predicted with the CoGEF method at the common B3LYP/6-31G* level of density functional theory are in excellent agreement with reactivity determined experimentally. Moreover, bond rupture forces obtained from CoGEF calculations are compared to experimentally measured forces and demonstrated to be reliable indicators of mechanochemical activity. This investigation validates the CoGEF method as a powerful tool for predicting mechanochemical reactivity, enabling its widespread adoption to support the developing field of polymer mechanochemistry. Secondarily, this study provides a contemporary catalog of over 100 mechanophores developed to date

Validation of the CoGEF Method as a Predictive Tool for Polymer Mechanochemistry

The development of force-responsive molecules called mechanophores is a central component of the field of polymer mechanochemistry. Mechanophores enable the design and fabrication of polymers for a variety of applications ranging from sensing to molecular release and self-healing materials. Nevertheless, an insufficient understanding of structure–activity relationships limits experimental development, and thus computation is necessary to guide the structural design of mechanophores. The constrained geometries simulate external force (CoGEF) method is a highly accessible and straightforward computational technique that simulates the effect of mechanical force on a molecule and enables the prediction of mechanochemical reactivity. Here, we use the CoGEF method to systematically evaluate every covalent mechanophore reported to date and compare the predicted mechanochemical reactivity to experimental results. Molecules that are mechanochemically inactive are also studied as negative controls. In general, mechanochemical reactions predicted with the CoGEF method at the common B3LYP/6-31G* level of density functional theory are in excellent agreement with reactivity determined experimentally. Moreover, bond rupture forces obtained from CoGEF calculations are compared to experimentally measured forces and demonstrated to be reliable indicators of mechanochemical activity. This investigation validates the CoGEF method as a powerful tool for predicting mechanochemical reactivity, enabling its widespread adoption to support the developing field of polymer mechanochemistry. Secondarily, this study provides a contemporary catalog of over 100 mechanophores developed to date

Fabrication and performance of selectively oxidized vertical-cavity lasers

Includes bibliographical references.We report the high yield fabrication and reproducible performance of selectively oxidized vertical-cavity surface emitting lasers. We show that linear oxidation rates of AlGaAs without an induction period allows reproducible fabrication of buried oxide current apertures within monolithic distributed Bragg reflectors. The oxide layers do not induce obvious crystalline defects, and continuous wave operation in excess of 650 h has been obtained. The high yield fabrication enables relatively high laser performance over a wide wavelength span. We observe submilliamp threshold currents over a wavelength range of up to 75 nm, and power conversion efficiencies at 1 mW output power of greater than 20% over a 50-nm wavelength range.The work at Sandia National Laboratories was supported in part by the United States DOE under contract No. DE-AC04-94AL85000

Improved AlGaInP-based red (670–690 nm) surface-emitting lasers with novel C-doped short-cavity epitaxial design

Includes bibliographical references (page 331).A modified epitaxial design leads to straightforward implementation of short (1λ) optical cavities and the use of C as the sole p-type dopant in AlGaInP/AlGaAs red vertical-cavity surface-emitting lasers (VCSELs). Red VCSELs fabricated into simple etched air posts operate continuous wave at room temperature at wavelengths between 670 and 690 nm, with a peak output power as high as 2.4 mW at 690 nm, threshold voltage of 2.2 V, and peak wallplug efficiency of 9%. These values are all significant improvements over previous results achieved in the same geometry with an extended optical cavity epitaxial design. The improved performance is due primarily to reduced optical losses and improved current constriction and dopant stability.This work was supported by the U.S. Department of Energy under Contract No. DE-AC04-94AL85000

Vectorial dissipative solitons in vertical-cavity surface-emitting Lasers with delays

We show that the nonlinear polarization dynamics of a vertical-cavity surface-emitting laser placed into an external cavity leads to the formation of temporal vectorial dissipative solitons. These solitons arise as cycles in the polarization orientation, leaving the total intensity constant. When the cavity round-trip is much longer than their duration, several independent solitons as well as bound states (molecules) may be hosted in the cavity. All these solutions coexist together and with the background solution, i.e. the solution with zero soliton. The theoretical proof of localization is given by the analysis of the Floquet exponents. Finally, we reduce the dynamics to a single delayed equation for the polarization orientation allowing interpreting the vectorial solitons as polarization kinks.Comment: quasi final resubmission version, 12 pages, 9 figure

Polarization investigation of a tunable high-speed short-wavelength bulk-micromachined MEMS-VCSEL

We report the investigation of the state of polarization (SOP) of a tunable vertical-cavity surface-emitting laser (VCSEL) operating near 850 nm with a mode-hop free single-mode tuning range of about 12 nm and an amplitude modulation bandwidth of about 5 GHz. In addition, the effect of a sub-wavelength grating on the device and its influence on the polarization stability and polarization switching has been investigated. The VCSEL with an integrated sub-wavelength grating shows a stable SOP with a polarization mode suppression ratio (PMSR) more than 35 dB during the tuning

Polarization characteristics, control, and modulation of vertical-cavity surface emitting lasers

The gain-dependent polarization properties of vertical-cavity surface emitting lasers and methods for polarization control and modulation are discussed. The partitioning of power between the two orthogonal eigen polarizations is shown to depend upon the relative spectral alignment of the nondegenerate polarization cavity resonances with the laser gain spectrum. A dominant polarization can thus be maintained by employing a blue-shifted offset of the peak laser gain relative to the cavity resonance wavelength. Alternatively, the polarization can be controlled through use of anisotropic transverse cavity geometries. The orthogonal eigen polarizations are also shown to enable polarization modulation. By exploiting polarization switching transitions in cruciform lasers, polarization modulation of the fundamental mode up to 50 MHz is demonstrated. At lower modulation frequencies, complementary digital polarized output or frequency doubling of the polarized output is obtained. Control and manipulation of vertical-cavity laser polarization may prove valuable for present and future applications

Cooperative coupling of ultracold atoms and surface plasmons

Cooperative coupling between optical emitters and light fields is one of the outstanding goals in quantum technology. It is both fundamentally interesting for the extraordinary radiation properties of the participating emitters and has many potential applications in photonics. While this goal has been achieved using high-finesse optical cavities, cavity-free approaches that are broadband and easy to build have attracted much attention recently. Here we demonstrate cooperative coupling of ultracold atoms with surface plasmons propagating on a plane gold surface. While the atoms are moving towards the surface they are excited by an external laser pulse. Excited surface plasmons are detected via leakage radiation into the substrate of the gold layer. A maximum Purcell factor of $\eta_\mathrm{P}=4.9$ is reached at an optimum distance of $z=250~\mathrm{nm}$ from the surface. The coupling leads to the observation of a Fano-like resonance in the spectrum.Comment: 9 pages, 4 figure