This work introduces the PYXAID program, developed for non-adiabatic molecular dynamics simulations in condensed matter systems. By applying classical path approximation to fewest switches surface hopping approach, we have an efficient computational tool that can be applied study photoinduced at ab initio level systems composed of hundreds atoms and involving thousands electronic states. The technique is used detail ultrafast relaxation hot electrons crystalline pentacene. simulated occurs...

In our previous work [J. Chem. Theory Comput. 2013, 9, 4959], we introduced the PYXAID program, developed for purpose of performing nonadiabatic molecular dynamics simulations in large-scale condensed matter systems. The methodological aspects and basic capabilities program have been extensively discussed. present work, perform a thorough investigation advanced namely, integration techniques time-dependent Schrodinger equation (TD-SE), decoherence corrections via decoherence-induced surface...

Long-lived coherences of excited states are notable for their positive effect on energy conversion mechanisms and efficiencies in photosynthetic complexes. Rational engineering such persistent could open a new way to increase rates man-made photovoltaic photocatalytic materials. Therefore, comprehensive understanding the fundamental principles behind long-lived is necessary. In this work we show that main factor determining decoherence magnitude nuclear-induced fluctuation gap between...

Charge carrier multiplication in organic heterojunction systems, a process known as singlet fission (SF), holds promise for development of solar cells with enhanced photon-to-electron yields, and therefore it is substantial fundamental interest. The efficiency photovoltaic devices based on this principle determined by complex dynamics involving key electronic states coupled to particular nuclear motions. Extensive experimental theoretical studies are dedicated topic, generating multiple...

In this work, we study the role of spin–orbit coupling (SOC) in nonradiative relaxation hot electrons and holes methylammonium lead perovskite, MAPbI3. For purpose, have developed nonadiabatic molecular dynamics method with two-component spinor wave functions that are solutions relativistic Kohn–Sham (KS) equations. We find SOC enhances contributions Pb(px) Pb(py) orbitals to conduction valence bands. As a result, KS become more sensitive nuclear motions, leading increased couplings....

Recent experimental studies demonstrated that photocatalytic CO2 reduction by Ru catalysts assembled on N-doped Ta2O5 surface is strongly dependent the nature of anchor group with which complexes are attached to substrate. We report a comprehensive atomistic analysis electron transfer dynamics in electroneutral Ru(di-X-bpy) (CO)2Cl2 X = COOH and PO3H2 N-Ta2O5 Nonadiabatic molecular simulations indicate faster anchors than groups, due larger nonadiabatic coupling. Quantum coherence...

Organic-inorganic lead-halide perovskites have received a revival of interest in the past few years as promising class materials for photovoltaic applications. Despite recent extensive research, role cations defining high performance these is not fully understood. Here, we conduct nonadiabatic molecular dynamics simulations to study and compare nonradiative hot carrier relaxation three perovskite materials: CH3NH3PbI3, HC(NH2)2PbI3, CsPbI3. It found that carriers band edges occurs on...

Excited state dynamics at the nanoscale requires treatment of systems involving hundreds and thousands atoms. In majority cases, depending on process under investigation, electronic structure component calculation constitutes computation bottleneck. We developed an efficient approach for simulating nonadiabatic molecular (NA-MD) large in framework self-consistent charge density functional tight binding (SCC-DFTB) method. SCC-DFTB is combined with fewest switches surface hopping (FSSH)...

Photochemical water splitting is a promising avenue to sustainable, clean energy and fuel production. Gallium nitride (GaN) its solid solutions are excellent photocatalytic materials; however, the efficiency of process low on pure GaN, cocatalysts required increase yields. We present first time-domain theoretical study initial steps GaN surface. Our state-of-the-art simulation technique, combining nonadiabatic molecular dynamics time-dependent density functional theory, allows us...

We report ab initio time-domain simulations of nonradiative electron–hole recombination and electronic dephasing in ideal defect-containing monolayer black phosphorus (MBP). Our calculations predict that the presence divacancy MBP (MBP-DV) substantially reduces rate, with time scales on order 1.57 ns. The luminescence line width 150 meV is 2.5 times larger than MBP-DV at room temperature, excellent agreement experiment. find driven by 450 cm–1 vibrational mode, whereas system a broad range...

Synergy of nonadiabatic molecular dynamics with real-time time-dependent density functional theory has led to significant progress in modeling excited-state nanoscale and condensed matter systems over the past decade. Nonadiabatic coupling (NAC) is central quantity such simulations, its accurate efficient evaluation an enduring challenge Kohn-Sham theory, particularly conjunction planewave basis sets projector augmented-wave (PAW) pseudopotentials because complexity PAW "all-electron" wave...

The "methodology discovery" library for quantum and classical dynamics simulations is presented. One of the major foci code on nonadiabatic molecular with model atomistic Hamiltonians treated same footing. essential aspects methodology, design philosophy, implementation are discussed. capabilities demonstrated a number test cases. It how can be used to study methodologies dynamics, as well tool performing detailed studies processes in systems. source additional information available Web at...

The outcomes of nonadiabatic molecular dynamics (NA-MD) calculations are modulated by the parameters entering time-dependent Schrödinger equation (TD-SE). adiabatic states commonly used as basis in which TD-SE is integrated. However, phase inconsistencies such along nuclear trajectories obtained NA-MD simulations may render wave function and other relevant properties ill-behaving, adversely affecting dynamics. This work illustrates consequence state Ehrenfest A simple phase-correction...

In this work, we report a simple, efficient, and scalable machine-learning (ML) approach for mapping non-self-consistent Kohn-Sham Hamiltonians constructed with one kind of density functional to the nearly self-consistent another functional. This is designed as fast surrogate Hamiltonian calculator use in long nonadiabatic dynamics simulations large atomistic systems. approach, input output features are matrices computed from different levels theory. We demonstrate that developed ML-based...

We present a new semiclassical approach for description of decoherence in electronically non-adiabatic molecular dynamics. The method is formulated on the grounds Ehrenfest dynamics and Meyer-Miller-Thoss-Stock mapping time-dependent Schrödinger equation onto fully classical Hamiltonian representation. introduce coherence penalty functional (CPF) that accounts effects by randomizing wavefunction phase penalizing development coherences regions strong coupling. performance demonstrated with...

This review focuses on recent developments in the field of nonadiabatic molecular dynamics (NA-MD), with particular attention given to condensed-matter systems. NA-MD simulations for small systems can be performed using high-level electronic structure (ES) calculations, methods accounting quantization nuclear motion, and fewer approximations dynamical methodology itself. Modeling imposes many limitations various aspects computations, requiring at levels theory-from ES, ways which coupling...

Non-adiabatic molecular dynamics simulations of non-radiative relaxation charge carriers in hybrid perovskites show that the carrier time can be considerably increased by halide mixing.

In this work, we report our implementation of several independent-trajectory mixed-quantum-classical (ITMQC) nonadiabatic dynamics methods based on exact factorization (XF) in the Libra package for and excited-state dynamics. Namely, surface hopping (SHXF), mixed quantum-classical (MQCXF), mean-field (MFXF) are introduced. Performance these is compared to that traditional schemes, such as fewest-switches (FSSH), branching-corrected (BCSH), simplified decay mixing (SDM), well conventional...

We developed molecular models describing the thermally initiated motion of nanocars, nanosized vehicles composed two to four spherical fullerene wheels chemically coupled a planar chassis, on metal surface. The simulations were aimed at reproducing qualitative features experimentally observed migration nanocars over gold crystals as determined by scanning tunneling microscopy. Coarse-grained-type dynamics carried out for species "Trimer" and "Nanotruck", simplified versions studied...

Clear mechanistic insights into excited state dynamics in thiolate-protected gold nanoclusters are vital for understanding the origin of photocatalytic enhancement via metal nanoparticles visible region. Extensive experimental studies on [Au25(SR)18]−1 nanocluster nonradiative relaxation reported very distinct time constants which span from femtosecond to nanosecond scale. In this work, relaxations [Au25(SH)18]−1 cluster investigated theoretically characterize electron dynamics. The core and...

Chalcogenide perovskites constitute an emerging class of promising photovoltaic materials that are stable and less toxic than popular lead-halide perovskites. Transition-metal chalcogenide doping the possible strategies for improving properties these via band gap engineering. At same time, can facilitate nonradiative charge-carrier recombination in materials, adversely affecting their properties. We report a systematic study electronic structure nonadiabatic dynamics transition-metal-...

Understanding microscopic mechanisms of motion artificial molecular machines is fundamentally important for scientific and technological progress. It known that electric field might strongly influence structures dynamic properties molecules at the nanoscale level. Specifically, it possible to induce conformational changes directional in many surface-bound by scanning tunneling microscopy (STM) experiments. Utilizing a recently developed theoretical method describe charge transfer phenomena...