Exploring the Global Reaction Coordinate for Retinal Photoisomerization: A Graph Theory-Based Machine Learning Approach.

Unraveling the reaction pathway of photoinduced reactions poses a great challenge owing to its complexity. Recently, graph theory-based machine learning combined with nonadiabatic molecular dynamics (NAMD) has been applied to obtain the global reaction coordinate of the photoisomerization of azobenzene. However, NAMD simulations are computationally expensive as they require calculating the nonadiabatic coupling vectors at each time step. Here, we showed that ab initio molecular dynamics (AIMD) can be used as an alternative to NAMD by choosing an appropriate initial condition for the simulation. We applied our methodology to determine a plausible global reaction coordinate of retinal photoisomerization, which is essential for human vision. On rank-ordering the internal coordinates, based on the mutual information (MI) between the internal coordinates and the HOMO energy, NAMD and AIMD give a similar trend. Our results demonstrate that our AIMD-based machine learning protocol for retinal is 1.5 times faster than that of NAMD to study reaction coordinates.

Photocatalytic activity of dual defect modified graphitic carbon nitride is robust to tautomerism: machine learning assisted ab initio quantum dynamics.

Two-dimensional graphitic carbon nitride (GCN) is a popular metal-free polymer for sustainable energy applications due to its unique structure and semiconductor properties. Dopants and defects are used to tune GCN, and dual defect modified GCN exhibits superior properties and enhanced photocatalytic efficiency in comparison to pristine or single defect GCN. We employ a multistep approach combining time-dependent density functional theory and nonadiabatic molecular dynamics (NAMD) with machine learning (ML) to investigate coupled structural and electronic dynamics in GCN over a nanosecond timescale, comparable to and exceeding the lifetimes of photo-generated charge carriers and photocatalytic events. Although frequent hydrogen hopping transitions occur among four tautomeric structures, the electron-hole separation and recombination processes are only weakly sensitive to the tautomerism. The charge separated state survives for about 10 ps, sufficiently long to enable photocatalysis. The employed ML-NAMD methodology provides insights into rare events that can influence excited state dynamics in the condensed phase and nanoscale materials and extends NAMD simulations from pico- to nanoseconds. The ab initio quantum dynamics simulation provides a detailed atomistic mechanism of photoinduced evolution of charge carriers in GCN and rationalizes how GCN remains photo-catalytically active despite its multiple isomeric and tautomeric forms.

Impact of large A-site cations on electron-vibrational interactions in 2D halide perovskites: Ab initio quantum dynamics.

Using ab initio nonadiabatic molecular dynamics, we study the effect of large A-site cations on nonradiative electron-hole recombination in two-dimensional Ruddlesden-Popper perovskites HA2APb2I7, HA = n-hexylammonium, A = methylammonium (MA), or guanidinium (GA). The steric hindrance created by large GA cations distorts and stiffens the inorganic Pb-I lattice, reduces thermal structural fluctuations, and maintains the delocalization of electrons and holes at ambient and elevated temperatures. The delocalized charges interact more strongly in the GA system than in the MA system, and the charge recombination is accelerated. In contrast, replacement of only some MA cations with GA enhances disorder and increases charge lifetime, as seen in three-dimensional perovskites. This study highlights the key influence of structural fluctuations and disorder on the properties of charge carriers in metal halide perovskites, providing guidance for tuning materials' optoelectronic performance.

Enhanced Charge Separation in Single Atom Cobalt Based Graphitic Carbon Nitride: Time Domain Ab Initio Analysis.

In recent years, single atom catalysts have been at the forefront of energy conversion research, particularly in the field of catalysis. Carbon nitrides offer great potential as hosts for stabilizing metal atoms due to their unique electronic structure. We use ab initio nonadiabatic molecular dynamics to study photoexcitation dynamics in single atom cobalt based graphitic carbon nitride. The results elucidate the positive effect of the doped cobalt atom on the electronic structure of GCN. Cobalt doping produces filled midgap states that serve as oxidation centers, advantageous for various redox reactions. The presence of midgap states enables the harvesting of longer wavelength photons, thereby extending the absorption range of solar light. Although doping accelerates charge relaxation overall, charge recombination is significantly slower than charge separation, creating beneficial conditions for catalysis applications. The simulations reveal the detailed microscopic mechanism underlying the improved performance of the doped system due to atomic defects and demonstrate an effective charge separation strategy to construct highly efficient and stable photocatalytic two-dimensional materials.

Lattice Distortion and Low-Frequency Anharmonic Phonons Suppress Charge Recombination in Lead Halide Perovskites upon Pseudohalide Doping: Time-Domain Ab Initio Analysis.

Perovskite solar cells have witnessed a surge in interest as a promising technology for low-cost, high-efficiency photovoltaics with certified power conversion efficiencies beyond 25%. However, their commercial development is hindered by poor stability and nonradiative losses that restrict their approach to the theoretical efficiency limit. Using ab initio nonadiabatic molecular dynamics, we demonstrate that nonradiative charge recombination is suppressed when the iodide in formamidinium lead iodide (FAPbI3) is partially replaced with pseudohalide anions (SCN-, BF4-, and PF6-). The replacement breaks the symmetry of the system and creates local structural distortion and dynamic disorder, decreasing electron-hole overlap and nonadiabatic electron-vibrational coupling. The charge carrier lifetime is found to increase with increased structural distortion and is the longest for PF6-. This work is fundamentally relevant to the design of high-performance perovskite materials for optoelectronic applications.

Control of Charge Carrier Relaxation at the Au/WSe2 Interface by Ti and TiO2 Adhesion Layers: Ab Initio Quantum Dynamics.

Phonon-mediated charge relaxation plays a vital role in controlling thermal transport across an interface for efficient functioning of two-dimensional (2D) nanostructured devices. Using a combination of nonadiabatic molecular dynamics with real-time time-dependent density functional theory, we demonstrate a strong influence of adhesion layers at the Au/WSe2 interface on nonequilibrium charge relaxation, rationalizing recent ultrafast time-resolved experiments. Ti oxide layers (TiOx) create a barrier to the interaction between Au and WSe2 and extend hot carrier lifetimes, creating benefits for photovoltaic and photocatalytic applications. In contrast, a metallic Ti layer accelerates the energy flow, as needed for efficient heat dissipation in electronic devices. The interaction of metallic Ti with WSe2 causes W-Se bond scissoring and pins the Fermi level. The Ti adhesion layer enhances the electron-phonon coupling due to an increased density of states and the light mass of the Ti atom. The conclusions are robust to presence of typical point defects. The atomic-scale ab initio analysis of carrier relaxation at the interfaces advances our knowledge in fabricating nanodevices with optimized electronic and thermal properties.

Charge carrier nonadiabatic dynamics in non-metal doped graphitic carbon nitride.

Graphitic carbon nitride (GCN) has attracted significant attention due to its excellent performance in photocatalytic applications. Non-metal doping of GCN has been widely used to improve the efficiency of the material as a photocatalyst. Using a combination of time-domain density functional theory with nonadiabatic molecular dynamics, we study the charge carrier dynamics in oxygen and boron doped GCN systems. The reported simulations provide a detailed time-domain mechanistic description of the charge separation and recombination processes that are of fundamental importance while evaluating the photovoltaic and photocatalytic performance of the material. The appearance of smaller energy gaps due to the presence of dopant states improves the visible light absorption range of the doped systems. At the same time, the nonradiative lifetimes are shortened in the doped systems as compared to the pristine GCN. In the case of boron doped at a carbon (B-C-GCN), the charge recombination time is very long as compared to the other two doped systems owing to the smaller electron-phonon coupling strength between the valence band maximum and the trap state. The results suggest B-C-GCN as the most suitable candidate among three doped systems studied in this work for applications in photocatalysis. This work sheds light into the influence of dopants on quantum dynamics processes that govern GCN performance and, thus, guides toward building high-performance devices in photocatalysis.

Excited State Dynamics in Dual-Defects Modified Graphitic Carbon Nitride.

Significant efforts are focused on defect-engineering of metal-free graphitic carbon nitride (g-C3N4) to amplify its efficacy. A conceptually new multidefect-modified g-C3N4 having simultaneously two or more defects has attracted strong attention for its enhanced photocatalytic properties. We model and compare the excited state dynamics in g-C3N4 with (i) nitrogen defects (N vacancy and CN group) and (ii) dual defects (N vacancy, CN group, and O doping) and show that the nonradiative recombination of charge carriers in these systems follows the Shockley-Read-Hall mechanism. The nitrogen defects create three midgap states that trap charges and act as recombination centers. The dual-defect modified systems exhibit superior properties compared with pristine g-C3N4 because the defects facilitate rapid charge separation and extend the spectrum of absorbed light. The system doped with O shows better performance due to enhanced carrier lifetime and higher oxidation potential caused by a downshifted valence band. The study provides guidance for rational design of stable and efficient photocatalytic materials.

Ab initio quantum dynamics of charge carriers in graphitic carbon nitride nanosheets.

Graphitic carbon nitride (g-C3N4), a metal-free and visible light responsive photocatalyst, has garnered much attention due to its wide range of applications. In order to elucidate the role of dimensionality on the properties of photo-generated charge carriers, we apply nonadiabatic (NA) molecular dynamics combined with time-domain density functional theory to investigate nonradiative relaxation of hot electrons and holes, and electron-hole recombination in monolayer and bulk g-C3N4. The nonradiative charge recombination occurs on a nanosecond timescale and is faster in bulk than the nanosheet, in agreement with the experiment. The difference arises due to the smaller energy gap and participation of additional vibrations in the bulk system. The long carrier lifetimes are favored by small NA coupling and rapid phonon-induced loss of quantum coherence between the excited and ground electronic states. Decoherence is fast because g-C3N4 is soft and undergoes large scale vibrations. The NA coupling is small since electrons and holes are localized on different atoms, and the electron-hole overlap is relatively small. Phonon-driven relaxation of hot electrons and holes takes 100-200 fs and is slightly slower at higher initial energies due to participation of fewer vibrational modes. This feature of two-dimensional g-C3N4 contrasts traditional three-dimensional semiconductors, which exhibit faster relaxation at higher energies due to larger density of states, and can be used to extract hot carriers to perform useful functions. The ab initio quantum dynamics simulations present a comprehensive picture of the photo-induced charge carrier dynamics in g-C3N4, guiding design of photovoltaic and photocatalytic devices.