Real-time Time-dependent Density Functional Theory Research Articles

Localization of hot carriers in Au144(SCH3)60 clusters doped with copper

Hot carriers (HCs) generated by visible light in metal nanostructures present significant potential for various applications. Nevertheless, comprehending HCs at a microscopic level has been a formidable challenge. This research delves into the spatial distribution of HCs within thiolate-protected Au144(SCH3)60 cluster doped with copper through real-time time-dependent density functional theory (rt-TDDFT). By accurately adjusting a Gaussian laser pulse to correspond to the dominant photoabsorption frequencies, we reveal the formation of hot electrons and hot holes. Throughout all the examined configurations, it was noted that copper doping creates a more pronounced influence on the distribution of hot holes compared to hot electrons, indicating the potential for precise control over HC generation in nanoscale systems with well-defined electronic structures.

Monitoring Density Redistribution at the Excited State in a Dual Emitting Molecule: An Analysis Based on Real-Time Density Functional Theory and Density Descriptors.

In this work, we computed and analyzed, by means of density-based descriptors, the real-time evolution of both the locally excited (LE) and charge-transfer (CT) excited states for the planar and twisted conformations of the DMABN (4-(N,N-dimethylamino)benzonitrile) molecule using real-time time-dependent density functional theory (DFT) and three different exchange-correlation energy functionals (EXC) belonging to the same family (the PBE one). Our results based on the analysis of density-based descriptors show that the underlying EXC modifies the evolution in time of the density. In particular, comparing the frequency of density reorganization computed with the three functionals (PBE, PBE0, and LC-PBE), we found that the frequency of electronic interconversion of the individual determinants involved during the dynamics increases from PBE to PBE0 and to LC-PBE. This allows us to show that there is a correlation between the delocalization of the electronic density and the frequency of reorganization. In particular, the greater the mean hole-electron distance during the dynamics, the lower is the frequency of density reorganization.

Efficient computational modeling of electronic stopping power of organic polymers for proton therapy optimization

This comprehensive study delves into the intricate interplay between protons and organic polymers, offering insights into proton therapy in cancer treatment. Focusing on the influence of the spatial electron density distribution on stopping power estimates, we employed real-time time-dependent density functional theory coupled with the Penn method. Surprisingly, the assumption of electron density homogeneity in polymers is fundamentally flawed, resulting in an overestimation of stopping power values at energies below 2 MeV. Moreover, the Bragg rule application in specific compounds exhibited significant deviations from experimental data around the stopping maximum, challenging established norms.

Laser-Induced Ultrafast Spin Injection in All-Semiconductor Magnetic CrI3/WSe2 Heterobilayer.

Spin injection stands out as a crucial method employed for initializing, manipulating, and measuring the spin states of electrons, which are fundamental to the creation of qubits in quantum computing. However, ensuring efficient spin injection while maintaining compatibility with standard semiconductor processing techniques is a significant challenge. Herein, we demonstrate the capability of inducing an ultrafast spin injection into a WSe2 layer from a magnetic CrI3 layer on a femtosecond time scale, achieved through real-time time-dependent density functional theory calculations upon a laser pulse. Following the peak of the magnetic moment in the CrI3 sublayer, the magnetic moment of the WSe2 layer reaches a maximum of 0.89 μB (per unit cell containing 4 WSe2 and 1 CrI3 units). During the spin dynamics, spin-polarized excited electrons transfer from the WSe2 layer to the CrI3 layer via type-II band alignment. The large spin splitting in conduction bands and the difference in the number of spin-polarized local unoccupied states available in the CrI3 layer lead to a net spin in the WSe2 layer. Furthermore, we confirmed that the number of available states, the spin-flip process, and the laser pulse parameters play important roles during the spin injection process. This work highlights the dynamic and rapid nature of spin manipulation in layered all-semiconductor systems, offering significant implications for the development and enhancement of quantum information processing technologies.

Reproducibility of real-time time-dependent density functional theory calculations of electronic stopping power in warm dense matter

Reproducibility of real-time time-dependent density functional theory calculations of electronic stopping power in warm dense matter

Carrier injection induced degradation of nitrogen passivated SiC–SiO2 interface simulated by time-dependent density functional theory

The performance of SiC-based metal-oxide-semiconductor field-effect transistors (MOSFETs) degrades seriously after a period of continuous operation. To directly understand this issue, we conduct real-time time-dependent density functional theory (TDDFT) simulations on a series of nitrogen passivated SiC–SiO2 interfaces to monitor the interaction between carriers and interface atoms. We find that the nitrogen passivation always leaves behind two local states near the VBM, which gives a chance to the strong interaction between channel carriers and C–N bonds, and finally results in the generation of C dangling bond defects. These processes are vividly presented and confirmed by the TDDFT simulation. Additionally, the results show that the new defects are more easily formed by the passivated C cluster than the passivated Si vacancy. These studies provide physical insights into the degradation mechanisms of working SiC MOSFETs, while simultaneously demonstrating the advantage of TDDFT as a crucial tool for investigating defect generation dynamics in semiconductor devices.

Ultrafast Chiral Precession of Spin and Orbital Angular Momentum Induced by Circularly Polarized Laser Pulse in Elementary Ferromagnets.

Despite spin (SAM) and orbital (OAM) angular momentum dynamics being well-studied in demagnetization processes, their components receive less focus. Here, we utilize real-time time-dependent density functional theory (rt-TDDFT) to unveil significant x and y components of SAM and OAM induced by circularly left (σ+) and right (σ-) polarized laser pulses in ferromagnetic Fe, Co, and Ni. Our results show that the magnitude of the OAM is an order of magnitude larger than that of the SAM, highlighting a stronger optical response from the orbital degrees of freedom of electrons. Intriguingly, σ+ and σ- pulses induce chirality in the precession of SAM and OAM, respectively, with clear associations with laser frequency and duration. Finally, we demonstrate the time scale of the OAM and SAM precession occurs even earlier than that of the demagnetization process and the OISTR effect. Our results provide detailed insight into the dynamics of SAM and OAM during and shortly after a polarized laser pulse.

Optical properties of Cu, Ag, and Au nanoparticles with different sizes and shapes

AbstractThe absorption spectra of various sizes of nanoparticles of copper (Cu), silver (Ag), and gold (Au) are theoretically investigated. The density functional theory (DFT), time‐dependent DFT (TDDFT), and real‐time TDDFT are used to demonstrate how size and shape affect their optical properties and how these are evolved as the number of atoms increases. For this reason, the focus was turned on almost spherical nanoparticles cut out from the corresponding crystal structure (called 0D), elongated ones (1D), and flattened ones (2D). The nature of the observed absorption peaks is further analyzed with the help of transition contribution maps and induced density plots which help us identify the emergence of probable plasmonic resonances as the size of the nanoparticles increases.

Two-dimensional electronic spectroscopy from first principles

The recent development of multidimensional ultrafast spectroscopy techniques calls for the introduction of computational schemes that allow for the simulation of such experiments and the interpretation of the corresponding results from a microscopic point of view. In this work, we present a general and efficient first-principles scheme to compute two-dimensional electronic spectroscopy maps based on real-time time-dependent density-functional theory. The interface of this approach with the Ehrenfest scheme for molecular dynamics enables the inclusion of vibronic effects in the calculations based on a classical treatment of the nuclei. The computational complexity of the simulations is reduced by the application of numerical advances such as branching techniques, undersampling, and a novel reduced phase cycling scheme, applicable for systems with inversion symmetry. We demonstrate the effectiveness of this method by applying it to prototypical molecules such as benzene, pyridine, and pyrene. We discuss the role of the approximations that inevitably enter the adopted theoretical framework and set the stage for further extensions of the proposed method to more realistic systems.

Plasmon induced hot carrier distribution in Ag20 -CO composite.

The interaction between plasmons and the molecules leads to the transfer of plasmon-induced hot carriers, presenting innovative opportunities for controlling chemical reactions on sub-femtosecond timescales. Through real-time time-dependent density functional theory simulations, we have investigated the enhancement of the electric field due to plasmon excitation and the subsequent generation and transfer of plasmon-induced hot carriers in a linear atomic chain of Ag20 and an Ag20 -CO composite system. By applying a Gaussian laser pulse tuned to align with the plasmon frequency, we observe a plasmon-induced transfer of hot electrons from the occupied states of Ag to the unoccupied molecular orbitals of CO. Remarkably, there is a pronounced accumulation of hot electrons and hot holes on the C and O atoms. This phenomenon arises from the electron migration from the inter-nuclear regions of the C-O bond towards the individual C and O atoms. The insights garnered from our study hold the potential to drive advancements in the development of more efficient systems for catalytic processes empowered by plasmonic interactions.

Squeezed Protons and Infrared Plasmonic Resonance Energy Transfer.

Unusual nuclear quantum effects may emerge near noble metal nanostructures such as squeezed vibrational states in molecular junctions and plasmonic resonance energy transfer in the infrared domain. Herein, nuclear quantum effects near heavy metals are studied by nuclear-electronic orbital density functional theory (NEO-DFT) with an effective core potential. For a quantum proton sandwiched between a pair of gold tips modeled by two Au6 clusters, NEO-DFT calculations suggest that the quantum proton density can be squeezed as the tip distance decreases. For an HF molecule placed near a one-dimensional Au nanowire composed of up to 34 Au atoms, real-time NEO time-dependent density functional theory (RT-NEO-TDDFT) shows that the infrared plasmonic motion within the Au nanowire may resonantly transfer electronic energy to the HF proton vibrational stretch mode. Overall, these calculations illustrate the advantages of the NEO approach for probing nuclear quantum effects, such as squeezed proton vibrational states and infrared plasmonic resonance energy transfer.

Time propagation of electronic wavefunctions using nonorthogonal determinant expansions.

The use of truncated configuration interaction in real-time time-dependent simulations of electron dynamics provides a balance of computational cost and accuracy, while avoiding some of the failures associated with real-time time-dependent density functional theory. However, low-order truncated configuration interaction also has limitations, such as overestimation of polarizability in configuration interaction singles, even when perturbative doubles are included. Increasing the size of the determinant expansion may not be computationally feasible, and so, in this work, we investigate the use of nonorthogonality in the determinant expansion to establish the extent to which higher-order substitutions can be recovered, providing an improved description of electron dynamics. Model systems are investigated to quantify the extent to which different methods accurately reproduce the (hyper)polarizability, including the high-harmonic generation spectrum of H2, water, and butadiene.

Plasmon-induced hot carrier distribution in a composite nanosystem: role of the adsorption site.

The generation of hot carriers (HCs) through the excitation of localized surface plasmon resonance (LSPR) in metal nanostructures is a fascinating phenomenon that fuels both fundamental and applied research. However, gaining insights into HCs at a microscopic level has posed a complex challenge, limiting our ability to create efficient nanoantennas that utilize these energized carriers. In this investigation, we employ real-time time-dependent density functional theory (rt-TDDFT) calculations to examine the creation and distribution of HCs within a model composite system consisting of a silver (Ag) nanodisk and a carbon monoxide (CO) molecule. We find that the creation and distribution of HCs are notably affected by the CO adsorption site. Particularly, when the CO molecule adsorbs onto the hollow site of the Ag nanodisk, it exhibits the highest potential among various composite systems in terms of structural stability, enhanced orbital hybridization, and HC generation and transfer. Utilizing a Gaussian laser pulse adjusted to match the LSPR frequency, we observe a marked buildup of hot electrons and hot holes on the C and O atoms. Conversely, the region encompassing the C-O bond exhibits a depletion of hot electrons and hot holes. We believe that these findings could have significant implications in the field of HC photocatalysis.

X-ray induced ultrafast charge transfer in thiophene-based conjugated polymers controlled by core-hole clock spectroscopy.

We explore ultrafast charge transfer (CT) resonantly induced by hard X-ray radiation in organic thiophene-based polymers at the sulfur K-edge. A combination of core-hole clock spectroscopy with real-time propagation time-dependent density functional theory simulations gives an insight into the electron dynamics underlying the CT process. Our method provides control over CT by a selective excitation of a specific resonance in the sulfur atom with monochromatic X-ray radiation. Our combined experimental and theoretical investigation establishes that the dominant mechanism of CT in polymer powders and films consists of electron delocalisation along the polymer chain occurring on the low-femtosecond time scale.

The impact of a dopant atom on the distribution of hot electrons and holes in Au-doped Ag nano-clusters.

The generation of hot carriers (HCs) through the excitation of localized surface plasmon resonance (LSPR) in metal nanostructures is a fascinating phenomenon that fuels both fundamental and applied research. In this study, we employ first principles real-time time-dependent density-functional theory (rt-TDDFT) calculations to elucidate the creation and distribution of HCs within Au-doped Ag nanoclusters: Ag11Cl3P7H21, Ag10AucoreCl3P7H21, and Ag10AusurfCl3P7H21 nanoclusters. Our findings indicate that adjustments in HC distribution are achievable through the Au dopant atom, and precise control of HC distribution is possible by manipulating the location of the Au dopant atom. When employing a Gaussian laser pulse tailored to match the LSPR frequency, a substantial accumulation of HCs in the Ag-P bond is observed. This finding suggests a weakening of the Ag-P bonds and, consequently, the initiation of bond stretching. We propose that these findings open up possibilities for tuning HCs in Au-doped chemically functionalized Ag nanoclusters.

Terahertz Laser Pulse Boosts Interlayer Spin Transfer in Two-Dimensional van der Waals Magnetic Heterostructures.

Light-induced ultrafast dynamics in two-dimensional (2D) magnetic systems demonstrate substantial advancements in spintronics. Here, using the real-time time-dependent density functional theory (rt-TDDFT), we applied laser pulses with various frequencies, from terahertz (THz) to optical pulse, to systematically study the interlayer spin transfer dynamics in 2D van der Waals nonmagnetic-ferromagnetic heterostructures, including graphene-Fe3GeTe2 (Gr/FGT) and silicene-Fe3GeTe2 (Si/FGT). Our results demonstrate that low-frequency THz pulses are particularly effective in facilitating interlayer spin injection from the ferromagnetic FGT layers to the Si or Gr layers. On the contrary, high-frequency optical pulses exhibit a minimal influence on this process. Such an effect is attributed to the low-frequency THz pulses inducing in-phase oscillations of the electron charge density around atomic centers, leading to a highly efficient interlayer spin transfer. Our results provide a new insight into ultrafast THz radiation control intralayer spin transfer and magnetic proximity dynamics in the 2D limit.

First-Principles Approach for Coupled Quantum Dynamics of Electrons and Protons in Heterogeneous Systems.

The coupled quantum dynamics of electrons and protons is ubiquitous in many dynamical processes involving light-matter interaction, such as solar energy conversion in chemical systems and photosynthesis. A first-principles description of such nuclear-electronic quantum dynamics requires not only the time-dependent treatment of nonequilibrium electron dynamics but also that of quantum protons. Quantum mechanical correlation between electrons and protons adds further complexity to such coupled dynamics. Here we extend real-time nuclear-electronic orbital time-dependent density functional theory (RT-NEO-TDDFT) to periodic systems and perform first-principles simulations of coupled quantum dynamics of electrons and protons in complex heterogeneous systems. The process studied is an electronically excited-state intramolecular proton transfer of o-hydroxybenzaldehyde in water and at a silicon (111) semiconductor-molecule interface. These simulations illustrate how environments such as hydrogen-bonding water molecules and an extended material surface impact the dynamical process on the atomistic level. Depending on how the molecule is chemisorbed on the surface, excited-state electron transfer from the molecule to the semiconductor surface can inhibit ultrafast proton transfer within the molecule. This Letter elucidates how heterogeneous environments influence the balance between the quantum mechanical proton transfer and excited electron dynamics. The periodic RT-NEO-TDDFT approach is applicable to a wide range of other photoinduced heterogeneous processes.

Watching the Interplay between Photoinduced Ultrafast Charge Dynamics and Nuclear Vibrations.

Here is presented the ultrafast hole-electron dynamics of photoinduced metal to ligand charge-transfer (MLCT) states in a Ru(II) complex, [Ru(dcbpy)2(NCS)2]4- (dcbpy = 4,4'-dicarboxy-2,2'-bipyridine), a photoactive molecule employed in dye sensitized solar cells. Via cutting-edge computational techniques, a tailored computational protocol is here presented and developed to provide a detailed analysis of the electronic manifold coupled with nuclear vibrations to better understand the nonradiative pathways and the resulting overall dye performances in light-harvesting processes (electron injection). Thus, the effects of different vibrational modes were investigated on both the electronic levels and charge transfer dynamics through a theoretical-computational approach. First, the linear response time-dependent density functional (LR-TDDFT) formalism was employed to characterize excitation energies and spacing among electronic levels (the electronic layouts). Then, to understand the ultrafast (femtosecond) charge dynamics on the molecular scale, we relied on the nonperturbative mean-field quantum electronic dynamics via real-time (RT-) TDDFT. Three vibrational modes were selected, representative for collective nuclear movements that can have a significant influence on the electronic structure: two involving NCS- ligands and one involving dcbpy ligands. As main results, we observed that such MLCT states, under vibrational distortions, are strongly affected and a faster interligand electron transfer mechanism is observed along with an increasing MLCT character of the adiabatic electronic states approaching closer in energy due to the vibrations. Such findings can help both in providing a molecular picture of multidimensional vibro-electronic spectroscopic techniques, used to characterize ultrafast coherent and noncoherent dynamics of complex systems, and to improve dye performances with particular attention to the study of energy or charge transport processes and vibronic couplings.

Trajectory sampling and finite-size effects in first-principles stopping power calculations

Real-time time-dependent density functional theory (TDDFT) is presently the most accurate available method for computing electronic stopping powers from first principles. However, obtaining application-relevant results often involves either costly averages over multiple calculations or ad hoc selection of a representative ion trajectory. We consider a broadly applicable, quantitative metric for evaluating and optimizing trajectories in this context. This methodology enables rigorous analysis of the failure modes of various common trajectory choices in crystalline materials. Although randomly selecting trajectories is common practice in stopping power calculations in solids, we show that nearly 30% of random trajectories in an FCC aluminum crystal will not representatively sample the material over the time and length scales feasibly simulated with TDDFT, and unrepresentative choices incur errors of up to 60%. We also show that finite-size effects depend on ion trajectory via “ouroboros” effects beyond the prevailing plasmon-based interpretation, and we propose a cost-reducing scheme to obtain converged results even when expensive core-electron contributions preclude large supercells. This work helps to mitigate poorly controlled approximations in first-principles stopping power calculations, allowing 1–2 order of magnitude cost reductions for obtaining representatively averaged and converged results.

Concerted Mechanism of Carrier Dynamics in Laser‐Excited Fen/(MgO)m(001) Heterostructures from Real‐Time Time‐Dependent DFT

AbstractUsing real‐time time‐dependent density functional theory (RT‐TDDFT), the electronic response of a Fen/(MgO)m(001) (n=1,3,5 and m=3,5,7) metal/insulator heterostructure to an optical excitation is calculated, considering laser frequencies below, near, and above the bandgap of the insulator and two directions of polarization. The spatial redistribution of electronic charge after illumination shows a strong dependence on the frequency and polarization direction of the laser pulse with a similar pattern for all thicknesses. The comparison of the layer‐resolved changes in occupation of the ground‐state orbitals after optical excitation obtained for Fen/(MgO)m(001) and bulk Fe reveals the origin of excited carriers in the heterostructures: In the central and interface Fe layers carriers are excited from states in the vicinity of the Fermi‐level to the conduction band of MgO. Simultaneously, excitations take place from the valence band of MgO to Fe states above the Fermi‐level. This concerted mechanism allows for an effective bidirectional relocation of excited carriers between the metallic and insulating subsystems in heterostructures with a thickness of several nanometers, providing an effective accumulation of hot carriers in the insulating layers, even at photon energies in the vicinity and below the bandgap of bulk MgO.