Ultrafast transient absorption spectroelectrochemistry: femtosecond to nanosecond excited-state relaxation dynamics of the individual components of an anthraquinone redox couple.

Many photoactivated processes involve a change in oxidation state during the reaction pathway and formation of highly reactive photoactivated species. Isolating these reactive species and studying their early-stage femtosecond to nanosecond (fs-ns) photodynamics can be challenging. Here we introduce a combined ultrafast transient absorption-spectroelectrochemistry (TA-SEC) approach using freestanding boron doped diamond (BDD) mesh electrodes, which also extends the time domain of conventional spectrochemical measurements. The BDD electrodes offer a wide solvent window, low background currents, and a tuneable mesh size which minimises light scattering from the electrode itself. Importantly, reactive intermediates are generated electrochemically, via oxidation/reduction of the starting stable species, enabling their dynamic interrogation using ultrafast TA-SEC, through which the early stages of the photoinduced relaxation mechanisms are elucidated. As a model system, we investigate the ultrafast spectroscopy of both anthraquinone-2-sulfonate (AQS) and its less stable counterpart, anthrahydroquinone-2-sulfonate (AH2QS). This is achieved by generating AH2QS in situ from AQS via electrochemical means, whilst simultaneously probing the associated early-stage photoinduced dynamical processes. Using this approach we unravel the relaxation mechanisms occurring in the first 2.5 ns, following absorption of ultraviolet radiation; for AQS as an extension to previous studies, and for the first time for AH2QS. AQS relaxation occurs via formation of triplet states, with some of these states interacting with the buffered solution to form a transient species within approximately 600 ps. In contrast, all AH2QS undergoes excited-state single proton transfer with the buffered solution, resulting in formation of ground state AHQS- within approximately 150 ps.

Effects of substituent position on aminobenzoate relaxation pathways in solution.

The negative effects of ultraviolet radiation (UVR) on human skin have led to the widespread use of sunscreens, i.e. skincare products containing UV filters to absorb, reflect or otherwise block UVR. The mechanisms by which UV filters dissipate energy following photoexcitation, i.e. their photodynamics, can crucially determine a molecule's performance as a sunscreen UV filter. In this work, we evaluate the effects of substituent position on the in-solution relaxation pathways of two derivates of methyl anthranilate (an ortho compound that is a precursor to the UV filter meradimate), meta- and para-methyl anthranilate, m-MA and p-MA, respectively. The photodynamics of m-MA were found to be sensitive to solvent polarity: its emission spectra show larger Stokes shifts with increasing polarity, and both the fluorescence quantum yield and lifetimes for m-MA increase in polar solvents. While the Stokes shifts for p-MA are much milder and more independent of solvent environment than those of m-MA, we find its fluorescence quantum yields to be sensitive not only to solvent polarity but to the hydrogen bonding character of the solvent. In both cases (m- and p-MA) we have found common computational methods to be insufficient to appropriately model the observed spectroscopic data, likely due to an inability to account for explicit solvent interactions, a known challenge in computational chemistry. Therefore, apart from providing insight into the photodynamics of anthranilate derivatives, the work presented here also provides a case study that may be of use to theoretical chemists looking to improve and develop explicit solvent computational methods.

Exploring the Photochemistry of an Ethyl Sinapate Dimer: An Attempt Toward a Better Ultraviolet Filter.

The photochemistry and photostability of a potential ultraviolet (UV) radiation filter, dehydrodiethylsinapate, with a broad absorption in the UVA region, is explored utilizing a combination of femtosecond time-resolved spectroscopy and steady-state irradiation studies. The time-resolved measurements show that this UV filter candidate undergoes excited state relaxation after UV absorption on a timescale of ~10 picoseconds, suggesting efficient relaxation. However, steady-state irradiation measurements show degradation under prolonged UV exposure. From a photochemical standpoint, this highlights the importance of considering both the ultrafast and "ultraslow" timescales when designing new potential UV filters.

ONETEP + TOSCAM: Uniting Dynamical Mean Field Theory and Linear-Scaling Density Functional Theory.

We introduce the unification of dynamical mean field theory (DMFT) and linear-scaling density functional theory (DFT), as recently implemented in ONETEP, a linear-scaling DFT package, and TOSCAM, a DMFT toolbox. This code can account for strongly correlated electronic behavior while simultaneously including the effects of the environment, making it ideally suited for studying complex and heterogeneous systems that contain transition metals and lanthanides, such as metalloproteins. We systematically introduce the necessary formalism, which must account for the nonorthogonal basis set used by ONETEP. In order to demonstrate the capabilities of this code, we apply it to carbon monoxide ligated iron porphyrin and explore the distinctly quantum-mechanical character of the iron 3d electrons during the process of photodissociation.

The ONETEP linear-scaling density functional theory program.

We present an overview of the onetep program for linear-scaling density functional theory (DFT) calculations with large basis set (plane-wave) accuracy on parallel computers. The DFT energy is computed from the density matrix, which is constructed from spatially localized orbitals we call Non-orthogonal Generalized Wannier Functions (NGWFs), expressed in terms of periodic sinc (psinc) functions. During the calculation, both the density matrix and the NGWFs are optimized with localization constraints. By taking advantage of localization, onetep is able to perform calculations including thousands of atoms with computational effort, which scales linearly with the number or atoms. The code has a large and diverse range of capabilities, explored in this paper, including different boundary conditions, various exchange-correlation functionals (with and without exact exchange), finite electronic temperature methods for metallic systems, methods for strongly correlated systems, molecular dynamics, vibrational calculations, time-dependent DFT, electronic transport, core loss spectroscopy, implicit solvation, quantum mechanical (QM)/molecular mechanical and QM-in-QM embedding, density of states calculations, distributed multipole analysis, and methods for partitioning charges and interactions between fragments. Calculations with onetep provide unique insights into large and complex systems that require an accurate atomic-level description, ranging from biomolecular to chemical, to materials, and to physical problems, as we show with a small selection of illustrative examples. onetep has always aimed to be at the cutting edge of method and software developments, and it serves as a platform for developing new methods of electronic structure simulation. We therefore conclude by describing some of the challenges and directions for its future developments and applications.

A molecular movie of ultrafast singlet fission.

The complex dynamics of ultrafast photoinduced reactions are governed by their evolution along vibronically coupled potential energy surfaces. It is now often possible to identify such processes, but a detailed depiction of the crucial nuclear degrees of freedom involved typically remains elusive. Here, combining excited-state time-domain Raman spectroscopy and tree-tensor network state simulations, we construct the full 108-atom molecular movie of ultrafast singlet fission in a pentacene dimer, explicitly treating 252 vibrational modes on 5 electronic states. We assign the tuning and coupling modes, quantifying their relative intensities and contributions, and demonstrate how these modes coherently synchronise to drive the reaction. Our combined experimental and theoretical approach reveals the atomic-scale singlet fission mechanism and can be generalized to other ultrafast photoinduced reactions in complex systems. This will enable mechanistic insight on a detailed structural level, with the ultimate aim to rationally design molecules to maximise the efficiency of photoinduced reactions.

Visualizing electrostatic gating effects in two-dimensional heterostructures.

The ability to directly monitor the states of electrons in modern field-effect devices-for example, imaging local changes in the electrical potential, Fermi level and band structure as a gate voltage is applied-could transform our understanding of the physics and function of a device. Here we show that micrometre-scale, angle-resolved photoemission spectroscopy1-3 (microARPES) applied to two-dimensional van der Waals heterostructures4 affords this ability. In two-terminal graphene devices, we observe a shift of the Fermi level across the Dirac point, with no detectable change in the dispersion, as a gate voltage is applied. In two-dimensional semiconductor devices, we see the conduction-band edge appear as electrons accumulate, thereby firmly establishing the energy and momentum of the edge. In the case of monolayer tungsten diselenide, we observe that the bandgap is renormalized downwards by several hundreds of millielectronvolts-approaching the exciton energy-as the electrostatic doping increases. Both optical spectroscopy and microARPES can be carried out on a single device, allowing definitive studies of the relationship between gate-controlled electronic and optical properties. The technique provides a powerful way to study not only fundamental semiconductor physics, but also intriguing phenomena such as topological transitions5 and many-body spectral reconstructions under electrical control.

Tensor network simulation of multi-environmental open quantum dynamics via machine learning and entanglement renormalisation.

The simulation of open quantum dynamics is a critical tool for understanding how the non-classical properties of matter might be functionalised in future devices. However, unlocking the enormous potential of molecular quantum processes is highly challenging due to the very strong and non-Markovian coupling of 'environmental' molecular vibrations to the electronic 'system' degrees of freedom. Here, we present an advanced but general computational strategy that allows tensor network methods to effectively compute the non-perturbative, real-time dynamics of exponentially large vibronic wave functions of real molecules. We demonstrate how ab initio modelling, machine learning and entanglement analysis can enable simulations which provide real-time insight and direct visualisation of dissipative photophysics, and illustrate this with an example based on the ultrafast process known as singlet fission.

Self-assembly of bis-salphen compounds: from semiflexible chains to webs of nanorings.

The recently-observed self-assembly of certain salphen-based compounds into neuron-like networks of microrings interconnected with nano-thin strings may suggest a new highly-potent tool for nanoscale patterning. However, the mechanism behind such phenomena needs to be clarified before they can be applied in materials design. Here we show that, in contrast with what was initially presumed, the emergence of a "rings-and-rods" pattern is unlikely to be explained by merging, collapse and piercing of vesicles as in previously reported cases of nanorings self-assembly via non-bonding interactions. We propose an alternative explanation: the compounds under study form a 1D coordination polymer, the fibres of which are elastic enough to fold into toroidal globules upon solvent evaporation, while being able to link separate chains into extended networks. This becomes possible because the structure of the compound's scaffold is found to adopt a very different conformation from that inferred in the original work. Based on ab initio and molecular dynamics calculations we propose a step-by-step description of self-assembly process of a supramolecular structure which explains all the observed phenomena in a simple and clear way. The individual roles of the compound' s scaffold structure, coordination centres, functional groups and solvent effects are also explained, opening a route to control the morphology of self-assembled networks and to synthesize new compounds exhibiting similar behaviour.

Evidence of Correlated Static Disorder in the Fenna-Matthews-Olson Complex.

Observation of excitonic quantum beats in photosynthetic antennae has prompted wide debate regarding the function of excitonic coherence in pigment-protein complexes. Much of this work focuses on the interactions of excitons with the femto-to-picosecond dynamical fluctuations of their environment. However, in experiments these effects can be masked by static disorder of the excited-state energies across ensembles, whose microscopic origins are challenging to predict. Here the excited-state properties of ∼2000 atom clusters of the Fenna-Matthews-Olson complex are simulated using a unique combination of linear-scaling density functional theory and constrained geometric dynamics. While slow, large amplitude protein motion leads to large variations in the Qy transitions of two pigments, we identify pigment-protein correlations that greatly reduce variations in the energy gap across the ensemble, which is consistent with experimental observations of suppressed inhomogeneous dephasing of quantum beats.

Nonradiative Step Facets in Semiconductor Nanowires.

One of the main advantages of nanowires for functional applications is their high perfection, which results from surface image forces that act on line defects such as dislocations, rendering them unstable and driving them out of the crystal. Here we show that there is a class of step facets that are stable in nanowires, with no long-range strain field or dislocation character. In zinc-blende semiconductors, they take the form of Σ3 (112) facets with heights constrained to be a multiple of three {111} monolayers. Density functional theory calculations show that they act as nonradiative recombination centers and have deleterious effects on nanowire properties. We present experimental observations of these defects on twin boundaries and twins that terminate inside GaAsP nanowires and find that they are indeed always multiples of three monolayers in height. Strategies to use the three-monolayer rule during growth to prevent their formation are discussed.

Chemically Selective Alternatives to Photoferroelectrics for Polarization-Enhanced Photocatalysis: The Untapped Potential of Hybrid Inorganic Nanotubes.

Linear-scaling density functional theory simulation of methylated imogolite nanotubes (NTs) elucidates the interplay between wall-polarization, bands separation, charge-transfer excitation, and tunable electrostatics inside and outside the NT-cavity. The results suggest that integration of polarization-enhanced selective photocatalysis and chemical separation into one overall dipole-free material should be possible. Strategies are proposed to increase the NT polarization for maximally enhanced electron-hole separation.

Determination of band offsets, hybridization, and exciton binding in 2D semiconductor heterostructures.

Combining monolayers of different two-dimensional semiconductors into heterostructures creates new phenomena and device possibilities. Understanding and exploiting these phenomena hinge on knowing the electronic structure and the properties of interlayer excitations. We determine the key unknown parameters in MoSe2/WSe2 heterobilayers by using rational device design and submicrometer angle-resolved photoemission spectroscopy (µ-ARPES) in combination with photoluminescence. We find that the bands in the K-point valleys are weakly hybridized, with a valence band offset of 300 meV, implying type II band alignment. We deduce that the binding energy of interlayer excitons is more than 200 meV, an order of magnitude higher than that in analogous GaAs structures. Hybridization strongly modifies the bands at Γ, but the valence band edge remains at the K points. We also find that the spectrum of a rotationally aligned heterobilayer reflects a mixture of commensurate and incommensurate domains. These results directly answer many outstanding questions about the electronic nature of MoSe2/WSe2 heterobilayers and demonstrate a practical approach for high spectral resolution in ARPES of device-scale structures.

Unravelling the Roles of Size, Ligands, and Pressure in the Piezochromic Properties of CdS Nanocrystals.

Understanding the effects of pressure-induced deformations on the optoelectronic properties of nanomaterials is important not only from the fundamental point of view but also for potential applications such as stress sensors and electromechanical devices. Here, we describe the novel insights into these piezochromic effects gained from using a linear-scaling density functional theory framework and an electronic enthalpy scheme, which allow us to accurately characterize the electronic structure of CdS nanocrystals with a zincblende-like core of experimentally relevant size. In particular, we focus on unravelling the complex interplay of size and surface (phenyl) ligands with pressure. We show that pressure-induced deformations are not simple isotropic scaling of the original structures and that the change in HOMO-LUMO gap with pressure results from two competing factors: (i) a bulk-like linear increase due to compression, which is offset by (ii) distortions and disorder and, to a lesser extent, orbital hybridization induced by ligands affecting the frontier orbitals. Moreover, we observe that the main peak in the optical absorption spectra is systematically red-shifted or blue-shifted, as pressure is increased up to 5 GPa, depending on the presence or absence of phenyl ligands. These heavily hybridize the frontier orbitals, causing a reduction in overlap and oscillator strength, so that at zero pressure, the lowest energy transition involves deeper hole orbitals than in the case of hydrogen-capped nanocrystals; the application of pressure induces greater delocalization over the whole nanocrystals bringing the frontier hole orbitals into play and resulting in an unexpected red shift for the phenyl-capped nanocrystals, in part caused by distortions. In response to a growing interest in relatively small nanocrystals that can be difficult to accurately characterize with experimental techniques, this work exemplifies the detailed understanding of structure-property relationships under pressure that can be obtained for realistic nanocrystals with state-of-the-art first-principles methods and used for the characterization and design of devices based on these and similar nanomaterials.

Linear-scaling density functional theory using the projector augmented wave method.

Quantum mechanical simulation of realistic models of nanostructured systems, such as nanocrystals and crystalline interfaces, demands computational methods combining high-accuracy with low-order scaling with system size. Blöchl's projector augmented wave (PAW) approach enables all-electron (AE) calculations with the efficiency and systematic accuracy of plane-wave pseudopotential calculations. Meanwhile, linear-scaling (LS) approaches to density functional theory (DFT) allow for simulation of thousands of atoms in feasible computational effort. This article describes an adaptation of PAW for use in the LS-DFT framework provided by the ONETEP LS-DFT package. ONETEP uses optimisation of the density matrix through in situ-optimised local orbitals rather than the direct calculation of eigenstates as in traditional PAW approaches. The method is shown to be comparably accurate to both PAW and AE approaches and to exhibit improved convergence properties compared to norm-conserving pseudopotential methods.

Tuning the role of charge-transfer states in intramolecular singlet exciton fission through side-group engineering.

Understanding the mechanism of singlet exciton fission, in which a singlet exciton separates into a pair of triplet excitons, is crucial to the development of new chromophores for efficient fission-sensitized solar cells. The challenge of controlling molecular packing and energy levels in the solid state precludes clear determination of the singlet fission pathway. Here, we circumvent this difficulty by utilizing covalent dimers of pentacene with two types of side groups. We report rapid and efficient intramolecular singlet fission in both molecules, in one case via a virtual charge-transfer state and in the other via a distinct charge-transfer intermediate. The singlet fission pathway is governed by the energy gap between singlet and charge-transfer states, which change dynamically with molecular geometry but are primarily set by the side group. These results clearly establish the role of charge-transfer states in singlet fission and highlight the importance of solubilizing groups to optimize excited-state photophysics.

Applications of large-scale density functional theory in biology.

Density functional theory (DFT) has become a routine tool for the computation of electronic structure in the physics, materials and chemistry fields. Yet the application of traditional DFT to problems in the biological sciences is hindered, to a large extent, by the unfavourable scaling of the computational effort with system size. Here, we review some of the major software and functionality advances that enable insightful electronic structure calculations to be performed on systems comprising many thousands of atoms. We describe some of the early applications of large-scale DFT to the computation of the electronic properties and structure of biomolecules, as well as to paradigmatic problems in enzymology, metalloproteins, photosynthesis and computer-aided drug design. With this review, we hope to demonstrate that first principles modelling of biological structure-function relationships are approaching a reality.

Multipurpose Black-Phosphorus/hBN Heterostructures.

Black phosphorus (BP) has recently emerged as a promising semiconducting two-dimensional material. However, its viability is threatened by its instability in ambient conditions and by the significant decrease of its band gap in multilayers. We show that one could solve all the aforementioned problems by interfacing BP with hexagonal boron nitride (hBN). To this end, we simulate large, rotated hBN/BP interfaces using linear-scaling density functional theory. We predict that hBN-encapsulation preserves the main electronic properties of the BP monolayer, while hBN spacers can be used to counteract the band gap reduction in stacked BP. Finally, we propose a model for a tunneling field effect transistor (TFET) based on hBN-spaced BP bilayers. Such BP TFETs would sustain both low-power and fast-switching operations, including negative differential resistance behavior with peak-to-valley ratios of the same order of magnitude as those encountered in transition metal dichalcogenide TFETs.

Pressure-Induced Amorphization and a New High Density Amorphous Metallic Phase in Matrix-Free Ge Nanoparticles.

Over the last two decades, it has been demonstrated that size effects have significant consequences for the atomic arrangements and phase behavior of matter under extreme pressure. Furthermore, it has been shown that an understanding of how size affects critical pressure-temperature conditions provides vital guidance in the search for materials with novel properties. Here, we report on the remarkable behavior of small (under ~5 nm) matrix-free Ge nanoparticles under hydrostatic compression that is drastically different from both larger nanoparticles and bulk Ge. We discover that the application of pressure drives surface-induced amorphization leading to Ge-Ge bond overcompression and eventually to a polyamorphic semiconductor-to-metal transformation. A combination of spectroscopic techniques together with ab initio simulations were employed to reveal the details of the transformation mechanism into a new high density phase-amorphous metallic Ge.

Hybrid MPI-OpenMP Parallelism in the ONETEP Linear-Scaling Electronic Structure Code: Application to the Delamination of Cellulose Nanofibrils.

We present a hybrid MPI-OpenMP implementation of Linear-Scaling Density Functional Theory within the ONETEP code. We illustrate its performance on a range of high performance computing (HPC) platforms comprising shared-memory nodes with fast interconnect. Our work has focused on applying OpenMP parallelism to the routines which dominate the computational load, attempting where possible to parallelize different loops from those already parallelized within MPI. This includes 3D FFT box operations, sparse matrix algebra operations, calculation of integrals, and Ewald summation. While the underlying numerical methods are unchanged, these developments represent significant changes to the algorithms used within ONETEP to distribute the workload across CPU cores. The new hybrid code exhibits much-improved strong scaling relative to the MPI-only code and permits calculations with a much higher ratio of cores to atoms. These developments result in a significantly shorter time to solution than was possible using MPI alone and facilitate the application of the ONETEP code to systems larger than previously feasible. We illustrate this with benchmark calculations from an amyloid fibril trimer containing 41,907 atoms. We use the code to study the mechanism of delamination of cellulose nanofibrils when undergoing sonification, a process which is controlled by a large number of interactions that collectively determine the structural properties of the fibrils. Many energy evaluations were needed for these simulations, and as these systems comprise up to 21,276 atoms this would not have been feasible without the developments described here.