Nonadiabatic Molecular Dynamics Simulations Research Articles

Ultrafast Charge and Proton Transfer in Doubly Ionized Ammonia Dimers.

We investigate the ultrafast energy and charge transfer processes between ammonia molecules following ionization reactions initiated by electron impact. Exploring ionization-induced processes in molecular clusters provides us with a detailed insight into the dynamics using experiments in the energy domain. We ionize the ammonia dimer with 200 eV electrons and apply the fragment ions coincident momentum spectroscopy and nonadiabatic molecular dynamics simulations. We identify two mechanisms leading to the doubly charged ammonia dimer. In the first one, a single molecule is ionized. This initiates an ultrafast proton transfer process, leading to the formation of the NH2+ + NH4+ pair. Alternatively, a dimer with a delocalized charge is formed dominantly via the intermolecular Coulombic decay, forming the NH3+·NH3+ dication. This dication further dissociates into two NH3+ cations. The ab initio calculations have reproduced the measured kinetic energy release of the ion pairs and revealed the dynamical processes following the double ionization.

Electronically Nonadiabatic H Atom Scattering from Low Miller Index Surfaces of Silver.

The reactivity of a surface depends strongly on the surface structure. To study the influence of surface structure on H atom adsorption, we performed inelastic scattering experiments and complementary electronically nonadiabatic molecular dynamics (MD) simulations for H atoms colliding with the three low Miller index surface facets of silver. Experiment reveals very similar energy loss distributions for all three investigated facets. However, for the (100) facet a dependence on the surface orientation is observed that is absent for the other two facets. The nonadiabatic MD simulations manage to describe the experiments well. Despite the observed insignificant influence of the surface geometry on the energy loss distributions, our simulations predict that the capability of the H atoms to penetrate the surface critically depends on the surface structure. The observed crystal orientation dependence of the energy loss distributions in the experiment for Ag(100) cannot be explained with our simulations, and we provide a discussion for a better theoretical description of this system to stimulate future computational investigations.

Time-Evolving Chirality Loss in Molecular Photodissociation Monitored by X-ray Circular Dichroism Spectroscopy.

The ultrafast photoinduced chirality loss of 2-iodobutane is studied theoretically by time- and frequency-resolved X-ray circular dichroism (TRXCD) spectroscopy. Following an optical excitation, the iodine atom dissociates from the chiral center, which we capture by quantum non-adiabatic molecular dynamics simulations. At variable time delays after the pump, the resonant X-ray pulse selectively probes the iodine and carbon atom involved in the chiral dissociation through a selected core-to-valence transition. The TRXCD signal at the iodine L1 edge accurately captures the timing of C-I photodissociation and thereby chirality loss, c.a 70 fs. The strong electric dipole-electric quadrupole (ED-EQ) response makes this signal particularly sensitive to vibronic coherence at the high X-ray regime. At the carbon K-edges, the signals monitor the molecular chirality of the 2-butyl radical photoproduct and the spin state of the iodine atom. The ED-EQ response is masked under the strong electric dipole-magnetic dipole response, making this signal intuitive for the electronic population. The evolution of the core electronic states and its chiral sensitivity is discussed. Overall, the element-specific TRXCD signal provides a detailed picture of molecular dynamics and offers a unique sensitive window into the time-dependent chirality of molecules.

Frenkel exciton photodynamics of self-assembled monolayers of azobiphenyls.

We performed computational simulations of the photodynamics of a self-assembled monolayer (SAM) of an azobenzene derivative (azobiphenyl, ABPT) on a gold surface. An excitonic approach was adopted in a semiempirical framework, which allowed us to consider explicitly the electronic degrees of freedom of 12 azobenzene chromophores. The surface hopping scheme was used for nonadiabatic molecular dynamics simulations. According to our results for an all trans-ABPT SAM, the excitation energy transfer between different chromophores, very fast in the ππ∗ manifold, does not occur between nπ∗ states. As a consequence, the excitation transfer does not play an important role in the quenching of the azobenzene photoisomerization in the SAM (experimentally observed and reproduced by our calculations) which, instead, has to be attributed to steric effects.

An "inverse" harpoon mechanism.

Electron-transfer reactions are ubiquitous in chemistry and biology. The electrons’ quantum nature allows their transfer across long distances. For example, in the well-known harpoon mechanism, electron transfer results in Coulombic attraction between initially neutral reactants, leading to a marked increase in the reaction rate. Here, we present a different mechanism in which electron transfer from a neutral reactant to a multiply charged cation results in strong repulsion that encodes the electron-transfer distance in the kinetic energy release. Three-dimensional coincidence imaging allows to identify such “inverse” harpoon products, predicted by nonadiabatic molecular dynamics simulations to occur between H2 and HCOH2+ following double ionization of isolated methanol molecules. These dynamics are experimentally initiated by single-photon double ionization with ultrafast extreme ultraviolet pulses, produced by high-order harmonic generation. A detailed comparison of measured and simulated data indicates that while the relative probability of long-range electron-transfer events is correctly predicted, theory overestimates the electron-transfer distance.

Thickness Dependent Ultrafast Charge Transfer in BP/MoS2 Heterostructure

AbstractConstructing high‐performance‐2D heterostructures and deciphering the underlying microscopic mechanism of carrier dynamics are crucial in optoelectronic and photovoltaic applications. Here, taking black phosphorus (BP)/MoS2 heterostructure with type‐II band alignment as a prototypical example, the ab initio nonadiabatic molecular dynamics simulations demonstrate that the interlayer carrier dynamics are thickness dependent. Specifically, the electron transfer from a monolayer (1L)‐BP to MoS2 occurs quickly within 54 fs. In contrast, hole transfer can only be observed within 1 ps with BP's layer number N ≥ 2, triggered by the excitation of low‐frequency acoustic phonon and interlayer shear and breathing phonon modes within 100 cm–1 that enhances the interlayer coupling. Particularly, the electron and hole transfer time exhibits respectively linear and exponential dependence on the layer number N of BP component. The present findings shed new light on improving the process of ultrafast carrier dynamics of 2D heterostructures for photoconversion.

Nonadiabatic molecular dynamics simulations based on time-dependent density functional tight-binding method.

Nonadiabatic excited state molecular dynamics underpin many photophysical and photochemical phenomena, such as exciton dynamics, and charge separation and transport. In this work, we present an efficient nonadiabatic molecular dynamics (NAMD) simulation method based on time-dependent density functional tight-binding (TDDFTB) theory. Specifically, the adiabatic electronic structure, an essential NAMD input, is described at the TDDFTB level. The nonadiabatic effects originating from the coupled motions of electrons and nuclei are treated by the trajectory surface hopping algorithm. To improve the computational efficiency, nonadiabatic couplings between excited states within the TDDFTB method are derived and implemented using an analytical approach. Furthermore, the time-dependent nonadiabatic coupling scalars are calculated based on the overlap between molecular orbitals rather than the Slater determinants to speed up the simulations. In addition, the electronic decoherence scheme and a state reassigned unavoided crossings algorithm, which has been implemented in the NEXMD software, are used to improve the accuracy of the simulated dynamics and handle trivial unavoided crossings. Finally, the photoinduced nonadiabatic dynamics of a benzene molecule are simulated to demonstrate our implementation. The results for excited state NAMD simulations of benzene molecule based on TDDFTB method compare well to those obtained with numerically expensive time-dependent density functional theory. The proposed methodology provides an attractive theoretical simulation tool for predicting the photophysical and photochemical properties of complex materials.

Effective lifetime of non-equilibrium carriers in semiconductors from non-adiabatic molecular dynamics simulations.

The lifetimes of non-equilibrium charge carriers in semiconductors calculated using non-adiabatic molecular dynamics often differ from experimental results by orders of magnitude. By revisiting the definition of carrier lifetime, we report a systematic procedure for calculating the effective carrier lifetime in semiconductor crystals under realistic conditions. The consideration of all recombination mechanisms and the use of appropriate carrier and defect densities are crucial to bridging the gap between modeling and measurements. Our calculated effective carrier lifetime of CH3NH3PbI3 agrees with experiments, and is limited by band-to-band radiative recombination and Shockley-Read-Hall defect-assisted non-radiative recombination, whereas the band-to-band non-radiative recombination is found to be negligible. The procedure is further validated by application to the compound semiconductors CdTe and GaAs, and thus can be applied in carrier lifetime simulations in other material systems.

Ultrafast Charge Transfer and Delayed Recombination in Graphitic-CN/WTe2 van der Waals Heterostructure: A Time Domain Ab Initio Study

In search of an efficient solar energy harvester, we herein performed a time domain density functional study coupled with nonadiabatic molecular dynamics (NAMD) simulation to gain atomistic insight into the charge carrier dynamics of a graphitic carbon nitride (g-CN)-tungsten telluride (WTe2) van der Waals heterostructure. Our NAMD study predicted ultrafast electron (589 fs) and hole-transfer (807 fs) dynamics in g-CN/WTe2 heterostructure and a delayed electron-hole recombination process (2.404 ns) as compared to that of the individual g-CN (3 ps) and WTe2 (0.55 ps) monolayer. The ultrafast charge transfer is due to strong electron-phonon coupling during the charge-transfer process while comparatively weak electron-phonon coupling, sufficient band gap, comparatively lower nonadiabatic coupling (NAC), and fast decoherence time slow down the electron-hole recombination process. The NAMD results of exciton relaxation dynamics are valuable for insightful understanding of charge carrier dynamics and in designing photovoltaic devices based on organic-inorganic 2D van der Waals heterostructures.

Multiscale Strategy for Predicting Radiation Chemistry in Polymers.

A primary mode for radiation damage in polymers arises from ballistic electrons that induce electronic excitations, yet subsequent chemical mechanisms are poorly understood. We develop a multiscale strategy to predict this chemistry starting from subatomic scattering calculations. Nonadiabatic molecular dynamics simulations sample initial bond-breaking events following the most likely excitations, which feed into semiempirical simulations that approach chemical equilibrium. Application to polyethylene reveals a mechanism explaining the low propensity to cross-link in crystalline samples.

First-principles studies of monolayers MoSi2N4 decorated with transition metal single-atom for visible light-driven high-efficient CO2 reduction by strain and electronic engineering

Solar-driven CO2 reduction into value-added hydrocarbons could promote CO2 utilization and solve related environmental issues, while the key lies in the modulation of the active site’s orbital electronic state. By performing first-principles calculations, we systematically explore MoSi2N4 decorated with 3d and 4d period transition metal single atoms (TMSAs) as efficient CO2 reduction photocatalysts and find that product selectivity is highly correlated with the d-band center of TMSAs. Compressive and tensile strains in mutually perpendicular directions are introduced in the horizontal plane to improve the catalytic performance. After filtering, V, Mn, and Ni were found to be the best TMSAs for CO, HCOOH, and CH4 production, respectively. Ni/MoSi2N4 under −6% tensile strain exhibited the lowest CO2 reduction limiting potential (UL) of 0.24 V. Notably, the time-dependent ab initio nonadiabatic molecular dynamics simulations were carried out to elucidate the photogenerated electron transport properties, where the photo-generated electrons can be efficiently transferred from MoSi2N4 to TMSAs active sites. We also identify that the applied strains affect the CO2 reduction performance by modulating the d-band center and valence electrons. These findings provide pioneering design schemes of precisely tailored photocatalytic systems for CO2 reduction under visible light.

Alkali metal doping in B–C3N4 extends carrier lifetime and increases the CO2 adsorption: DFT study and time-domain Ab initio analysis

Carbon nitride (C3N4) has been widely used in photocatalytic applications. Its performance is unsatisfactory due to high band gap. In order to address these challenges, we have investigated the effect of alkali metals (Na, Li) on B-doped C3N4 having nitrogen vacancy (Nv). DFT calculations show that doping of alkali metals into B doped C3N4 (B–C3N4) can decrease its band gap. Na atom doped into the surface of B–C3N4 transfers all of its charge to atoms on the surface. There is transfer of charge from surface to CO2 when it is adsorbed on Na/B–C3N4. In Li doped B– C3N4 system (Li/B– C3N4), Li atom form bond with two N atoms. There is transfer of charge from Li–N bonds to CO2, which would facilitate the stronger adsorption of CO2. Using nonadiabatic molecular dynamics (NAMD) simulations, we show that recombination rate of charge carriers decreases in alkali doped samples. Our results provide new insight into tuning of band gap of C3N4 in visible/infrared region of the spectrum. Na/B-co-doped C3N4 is considered to be an efficient photocatalyst as it has lowest band gap, shows reasonable adsorption for CO2 and lifetime of charge carriers is extended by a factor of three as compared to B–C3N4.

Photoinduced small electron polarons generation and recombination in hematite

Polarons generally affect adversely the photochemical and photophysical properties of transition metal oxides. However, the excited-state dynamics of polarons are not fully established to date and thus require an atomistic understanding. We focus on α-Fe2O3 with photoexcitation, electron injection, and heterovalent doping as the small polaron models, and conduct simulations of ab initio adiabatic molecular dynamics (AIMD) and nonadiabatic molecular dynamics (NA-MD). The elaborately designed AIMD simulations show that localization of electron at a single Fe site is an adiabatic and ultrafast process within sub-15 fs. Fe2O3 doping with an electron or a Si and Ti dopant forms a localized electron polaron while photoexcitation forms localized electron and hole polarons simultaneously, leading to diverse electron–hole recombination dynamics. NA-MD simulations demonstrate that recombination of an electron polaron created by doping with a delocalized hole at the valence band maximum of α-Fe2O3 takes place around 5 ps, while recombination between a pair of small electron and hole polarons in photoexcited Fe2O3 delays to about 110 ps owing to weak NA coupling and fast decoherence process. The ultrafast formation of small electron polarons in α-Fe2O3 impedes the accumulation of delocalized holes in the valence band that directly participate in water oxidation at photoanodes. The detrimental effect can be partially circumvented in photoexcited Fe2O3 for slowing electron–hole recombination despite polarons may retain low charge mobility. These findings provide a fundamental understanding of the excited-state dynamics of small electron polaron in α-Fe2O3 and may help design efficient transition metal oxides photoanodes.

Raw data of first-principles calculations for "Effective Lifetime of Non-Equilibrium Carriers in Semiconductors from Non-Adiabatic Molecular Dynamics Simulations"

Raw data of first-principles calculations for "Effective Lifetime of Non-Equilibrium Carriers in Semiconductors from Non-Adiabatic Molecular Dynamics Simulations"

Ultrafast charge generation in a homogenous polymer domain

Efficient charge generation contributes greatly to the high performance of organic photovoltaic devices. The mechanism of charge separation induced by heterojunction has been widely accepted. However, how and why free charge carriers can generate in homogenous polymer domains remains to be explored. In this work, the extended tight-binding SSH model, combined with the non-adiabatic molecular dynamics simulation, is used to construct the model of a polymer array in an applied electric field and simulate the evolution of an excited state. It is found that under a very weak external electric field 5.0 × 10−3 V/Å, the excited state can evolve directly into spatially separated free charges at the femtosecond scale, and the efficiency is up to 97%. The stacking structure of the polymer array leads to intermolecular electron mutualization and forms intermolecular coupling. This interaction tends to delocalize the excited states in organic semiconductors, competing with the localization caused by electron–phonon coupling. Excitons within the homogenous polymer domains have lower binding energy, less energy dissipation, and ultrafast charge separation. Therefore, the initial excited state can evolve directly into free carriers under a very weak electric field. This finding provides a reasonable explanation for ultrafast charge generation in pure polymer phases and is consistent with the fact that delocalization always coexists with ultrafast charge generation. Moreover, the devices based on homogenous polymer domains are supposed to be stress-sensitive and performance-anisotropic since the above two interactions have contrary effects and work in perpendicular directions. This work is expected to bring inspiration for the design of organic functional materials and devices.

Excited-State Distortions Promote the Photochemical 4π-Electrocyclizations of Fluorobenzenes via Machine Learning Accelerated Photodynamics Simulations.

Benzene fluorination increases chemoselectivities for Dewar-benzenes via 4π-disrotatory electrocyclization. However, the origin of the chemo- and regioselectivities of fluorobenzenes remains unexplained because of the experimental limitations in resolving the excited-state structures on ultrafast timescales. The computational cost of multiconfigurational nonadiabatic molecular dynamics simulations is also currently cost-prohibitive. We now provide high-fidelity structural information and reaction outcome predictions with machine-learning-accelerated photodynamics simulations of a series of fluorobenzenes, C6 F6-n Hn , n=0-3, to study their S1 →S0 decay in 4 ns. We trained neural networks with XMS-CASPT2(6,7)/aug-cc-pVDZ calculations, which reproduced the S1 absorption features with mean absolute errors of 0.04 eV (<2 nm). The predicted nonradiative decay constants for C6 F4 H2 , C6 F6 , C6 F3 H3 , and C6 F5 H are 116, 60, 28, and 12 ps, respectively, in broad qualitative agreement with the experiments. Our calculations show that a pseudo Jahn-Teller distortion of fluorinated benzenes leads to an S1 local-minimum region that extends the excited-state lifetimes of fluorobenzenes. The pseudo Jahn-Teller distortions reduce when fluorination decreases. Our analysis of the S1 dynamics shows that the pseudo-Jahn-Teller distortions promote an excited-state cis-trans isomerization of a πC-C bond. We characterized the surface hopping points from our NAMD simulations and identified instantaneous nuclear momentum as a factor that promotes the electrocyclizations.

The Photocycle of Bacteriophytochrome Is Initiated by Counterclockwise Chromophore Isomerization.

Photoactivation of bacteriophytochrome involves a cis–trans photoisomerization of a biliverdin chromophore, but neither the precise sequence of events nor the direction of the isomerization is known. Here, we used nonadiabatic molecular dynamics simulations on the photosensory protein dimer to resolve the isomerization mechanism in atomic detail. In our simulations the photoisomerization of the D ring occurs in the counterclockwise direction. On a subpicosecond time scale, the photoexcited chromophore adopts a short-lived intermediate with a highly twisted configuration stabilized by an extended hydrogen-bonding network. Within tens of picoseconds, these hydrogen bonds break, allowing the chromophore to adopt a more planar configuration, which we assign to the early Lumi-R state. The isomerization process is completed via helix inversion of the biliverdin chromophore to form the late Lumi-R state. The mechanistic insights into the photoisomerization process are essential to understand how bacteriophytochrome has evolved to mediate photoactivation and to engineer this protein for new applications.

Monitoring substrate-induced electron–phonon coupling at interfaces of 2D organic/inorganic van der Waals heterostructures with in situ Raman spectroscopy

Multifunctional devices based on 2D organic/inorganic van der Waals heterostructures (2D OIHs) exhibit excellent properties due to extensive and flexible structural tunability. However, how to precisely regulate devices via in situ monitoring technique remains a great challenge, and corresponding development is still in its infancy. In this Letter, we show that Raman spectroscopy can serve as an effective in situ detection strategy to systematically observe the interfacial electron–phonon coupling (IEPC) between substrate and 2D OIHs. Combining non-adiabatic molecular dynamics simulations with ultrafast spectroscopy, we reveal that the different strengths of IEPC between substrates and 2D OIHs can directly modulate the photocarrier lifetimes of inorganic 2D materials, and therefore, indirectly modify the Raman-sensitive photo-induced charge transfer processes at the interface of 2D OIHs. Further in situ Raman evidence demonstrates the unique advantage of Raman spectroscopy with high sensitivity to monitor different substrate-induced IEPC under variable temperature.

The ΔSCF method for non-adiabatic dynamics of systems in the liquid phase.

Computational studies of ultrafast photoinduced processes give valuable insights into the photochemical mechanisms of a broad range of compounds. In order to accurately reproduce, interpret, and predict experimental results, which are typically obtained in a condensed phase, it is indispensable to include the condensed phase environment in the computational model. However, most studies are still performed in vacuum due to the high computational cost of state-of-the-art non-adiabatic molecular dynamics (NAMD) simulations. The quantum mechanical/molecular mechanical (QM/MM) solvation method has been a popular model to perform photodynamics in the liquid phase. Nevertheless, the currently used QM/MM embedding techniques cannot sufficiently capture all solute-solvent interactions. In this Perspective, we will discuss the efficient ΔSCF electronic structure method and its applications with respect to the NAMD of solvated compounds, with a particular focus on explicit quantum mechanical solvation. As more research is required for this method to reach its full potential, some challenges and possible directions for future research are presented as well.

Chemistry without the Born-Oppenheimer approximation.

Chemistry without the Born-Oppenheimer approximation.