Use of QM/MM Surface Hopping Simulations to Understand Thermally Activated Rare-Event Nonadiabatic Transitions in the Condensed Phase.

We implement a rare-event sampling scheme for quantifying the rate of thermally activated nonadiabatic transitions in the condensed phase. Our Quantum mechanics/molecular mechanics (QM/MM) methodology uses the recently developed Interface for NonAdiabatic QM/MM in Solvent (INAQS) package to interface an elementary electronic structure package and a popular open-source molecular dynamics software (GROMACS) to simulate an electron transfer event between two stationary ions in a solution of acetonitrile solvent molecules. Nonadiabatic effects are implemented through a surface hopping scheme, and our simulations allow further quantitative insight into the participation ratio of a solvent and the effect of ion separation distance as far as facilitating electron transfer. We also demonstrate that the standard gas-phase approaches for treating frustrated hops and velocity reversal must be refined when working in the condensed phase with many degrees of freedom. The code and methodology developed here can be easily expanded upon and modified to incorporate other systems and should provide a great deal of new insight into a wide variety of condensed phase nonadiabatic phenomena.

InGaN micro-LED array with integrated emission and detection functions for color detection application.

InGaN-based micro-LEDs can detect and emit optical signals simultaneously, owing to their overlapping emission and absorption spectra, enabling color detection. In this paper, we fabricated a green InGaN-based micro-LED array with integrated emission and detection functions. On the back side of the integrated device, when the 80 µm micro-LED emitted light, the 200 µm LED could receive reflected light to accomplish color detection. The spacing between the 80 µm and the 200 µm micro-LEDs was optimized to be 1 mm to reduce the effect of the direct light transmitted through the n-GaN layer without reflection. The integrated device shows good detection performance for different colors and skin colors, even in a dark environment. In addition, light can be emitted from the top side of the device. Utilization of light from both sides of the integrated device provides the possibility of its application in display, communication, and detection on the different sides.

10-Gbps visible light communication in a 10-m free space based on violet series-biased micro-LED array and distance adaptive pre-equalization.

In this paper, we fabricated a 3×3 violet series-biased micro-LED array with high-output optical power and applied it in high-speed and long-distance visible light communication. By employing the orthogonal frequency division multiplexing modulation scheme, distance adaptive pre-equalization, and a bit-loading algorithm, record data rates of 10.23 Gbps, 10.10 Gbps, and 9.51 Gbps were achieved at 0.2 m, 1 m, and 10 m, respectively, below the forward error correction limit of 3.8×10-3. To the best of our knowledge, these are the highest data rates achieved by violet micro-LEDs in free space and the first communication demonstration beyond 9.5 Gbps at 10 m using micro-LEDs.

Vertical stack integration of blue and yellow InGaN micro-LED arrays for display and wavelength division multiplexing visible light communication applications.

In this work, we demonstrated a convenient and reliable method to realize the vertical stack integration of the blue and yellow InGaN micro-LED arrays. The standard white and color-tunable micro-light sources can be achieved by adjusting the current densities injection of the micro-LEDs. The spectra cover violet, standard white, cyan, etc., showing an excellent color-tunable property. And the mixed standard white light can be separated into red-green-blue three primary colors through the color filters to realize full-color micro-LED display with a color gamut of 75% NTSC. Besides, the communication capability of the integrated micro-LED arrays as visible light communication (VLC) transmitters is demonstrated with a maximum total data rate of 2.35 Gbps in the wavelength division multiplexing (WDM) experimental set-up using orthogonal frequency division multiplexing modulation. In addition, a data rate of 250 Mbps is also realized with the standard white light using on-off keying (OOK) modulation. This integrated device shows great potential in full-color micro-LED display, color-tunable micro-light sources, and high-speed WDM VLC multifunctional applications.

High bandwidth series-biased green micro-LED array toward 6 Gbps visible light communication.

In this Letter, a record modulation bandwidth of 1.31 GHz was achieved by a 10 µm c-plane green micro light emitting diode (micro-LED) at a current density of 41.4 kA/cm2. Furthermore, by designing a series-biased 20 µm micro-LED with higher light output power, combined with an orthogonal frequency division multiplexing modulation scheme, a maximum data rate of 5.789 Gbps was achieved at a free-space transmission distance of 0.5 m. This work demonstrates the prospect of c-plane polar green micro-LED in ultrahigh-speed visible light communication, which is expected to realize a high-performance wireless system in the future.

Methods to Calculate Electronic Excited-State Dynamics for Molecules on Large Metal Clusters with Many States: Ensuring Fast Overlap Calculations and a Robust Choice of Phase.

We present an efficient set of methods for propagating excited-state dynamics involving a large number of configuration interaction singles (CIS) or Tamm-Dancoff approximation (TDA) single-reference excited states. Specifically, (i) following Head-Gordon et al., we implement an exact evaluation of the overlap of singly-excited CIS/TDA electronic states at different nuclear geometries using a biorthogonal basis and (ii) we employ a unified protocol for choosing the correct phase for each adiabat at each geometry. For many-electron systems, the combination of these techniques significantly reduces the computational cost of integrating the electronic Schrodinger equation and imposes minimal overhead on top of the underlying electronic structure calculation. As a demonstration, we calculate the electronic excited-state dynamics for a hydrogen molecule scattering off a silver metal cluster, focusing on high-lying excited states, where many electrons can be excited collectively and crossings are plentiful. Interestingly, we find that the high-lying, plasmon-like collective excitation spectrum changes with nuclear dynamics, highlighting the need to simulate non-adiabatic nuclear dynamics and plasmonic excitations simultaneously. In the future, the combination of methods presented here should help theorists build a mechanistic understanding of plasmon-assisted charge transfer and excitation energy relaxation processes near a nanoparticle or metal surface.

Beyond 25 Gbps optical wireless communication using wavelength division multiplexed LEDs and micro-LEDs.

In this Letter, high-speed optical wireless communication (OWC) with three light-emitting diodes (LED) and five micro-LEDs (µLEDs) is proposed as a proof-of-concept wavelength division multiplexing (WDM) system. It covers a wide spectrum from deep ultraviolet (UV) to visible light and thus could offer both visible light communication (VLC) and UV communication simultaneously. An aggregated data rate of up to 25.20 Gbps over 25 cm free space is achieved, which, to the best of our knowledge, is the highest data rate for LED-based OWC ever reported. Among them, the five µLEDs offer a data rate of up to 18.43 Gbps, which, to the best of our knowledge, is the highest data rate for µLED-based OWC so far. It shows the superiority and potential of µLEDs for WDM-OWC. Additionally, a data rate of 20.11 Gbps for VLC is achieved.

Nonadiabatic Dynamics at Metal Surfaces: Fewest Switches Surface Hopping with Electronic Relaxation.

A new scheme is proposed for modeling molecular nonadiabatic dynamics near metal surfaces. The charge-transfer character of such dynamics is exploited to construct an efficient reduced representation for the electronic structure. In this representation, the fewest switches surface hopping (FSSH) approach can be naturally modified to include electronic relaxation (ER). The resulting FSSH-ER method is valid across a wide range of coupling strengths as supported by tests applied to the Anderson-Holstein model for electron transfer. Future work will combine this scheme with ab initio electronic structure calculations.

Configuration interaction approaches for solving quantum impurity models.

We develop several configuration interaction approaches for characterizing the electronic structure of an adsorbate on a metal surface (at least in model form). When one can separate the adsorbate from the substrate, these methods can achieve a reasonable description of adsorbate on-site electron-electron correlation in the presence of a continuum of states. While the present paper is restricted to the Anderson impurity model, there is hope that these methods can be extended to ab initio Hamiltonians and provide insight into the structure and dynamics of molecule-metal surface interactions.

A Robust and Unified Solution for Choosing the Phases of Adiabatic States as a Function of Geometry: Extending Parallel Transport Concepts to the Cases of Trivial and Near-Trivial Crossings.

We investigate a simple and robust scheme for choosing the phases of adiabatic electronic states smoothly (as a function of geometry) so as to maximize the performance of ab initio non-adiabatic dynamics methods. Our approach is based upon consideration of the overlap matrix (U) between basis functions at successive points in time and selecting the phases so as to minimize the matrix norm of log(U). In so doing, one can extend the concept of parallel transport to cases with sharp curve crossings. We demonstrate that this algorithm performs well under extreme situations where dozens of states cross each other either through trivial crossings (where there is zero effective diabatic coupling), or through non-trivial crossings (when there is a non-zero diabatic coupling), or through a combination of both. In all cases, we compute the time-derivative coupling matrix elements (or equivalently non-adiabatic derivative coupling matrix elements) that are as smooth as possible. Our results should be of interest to all who are interested in either non-adiabatic dynamics, or more generally, parallel transport in large systems.

A practical ansatz for evaluating the electronic friction tensor accurately, efficiently, and in a nearly black-box format.

It is well-known that under conditions of fast electronic equilibration and weak nonadiabaticity, nonadiabatic effects induced by electron-hole pair excitations can be partly incorporated through a frictional force. However, ab initio computation of the electronic friction tensor suffers from numerical instability and usually demands a convergence check. In this study, we present an efficient and accurate interpolation method for computing the electronic friction tensor in a nearly black-box manner as appropriate for molecular dynamics. In almost all cases, our method agrees quite well with the exact friction tensor which is available for several quadratic Hamiltonians. As such, we outperform more conventional approaches that are based on the introduction of a broadening parameter. Future work will implement this interpolation approach within ab initio software packages.

Localized diabatization applied to excitons in molecular crystals.

Traditional ab initio electronic structure calculations of periodic systems yield delocalized eigenstates that should be understood as adiabatic states. For example, excitons are bands of extended states which superimpose localized excitations on every lattice site. However, in general, in order to study the effects of nuclear motion on exciton transport, it is standard to work with a localized description of excitons, especially in a hopping regime; even in a band regime, a localized description can be helpful. To extract localized excitons from a band requires essentially a diabatization procedure. In this paper, three distinct methods are proposed for such localized diabatization: (i) a simple projection method, (ii) a more general Pipek-Mezey localization scheme, and (iii) a variant of Boys diabatization. Approaches (i) and (ii) require localized, single-particle Wannier orbitals, while approach (iii) has no such dependence. These methods should be very useful for studying energy transfer through solids with ab initio calculations.