Renormalization group analysis of the Anderson model on random regular graphs.

We present a renormalization group (RG) analysis of the problem of Anderson localization on a random regular graph (RRG) which generalizes the RG of Abrahams, Anderson, Licciardello, and Ramakrishnan to infinite-dimensional graphs. The RG equations necessarily involve two parameters (one being the changing connectivity of subtrees), but we show that the one-parameter scaling hypothesis is recovered for sufficiently large system sizes for both eigenstates and spectrum observables. We also explain the nonmonotonic behavior of dynamical and spectral quantities as a function of the system size for values of disorder close to the transition, by identifying two terms in the beta function of the running fractal dimension of different signs and functional dependence. Our theory provides a simple and coherent explanation for the unusual scaling behavior observed in numerical data of the Anderson model on RRG and of many-body localization.

Absolute energy levels of liquid water from many-body perturbation theory with effective vertex corrections.

We demonstrate the importance of addressing the Γ vertex and thus going beyond the GW approximation for achieving the energy levels of liquid water in many-body perturbation theory. In particular, we consider an effective vertex function in both the polarizability and the self-energy, which does not produce any computational overhead compared with the GW approximation. We yield the band gap, the ionization potential, and the electron affinity in good agreement with experiment and with a hybrid functional description. The achieved electronic structure and dielectric screening further lead to a good description of the optical absorption spectrum, as obtained through the solution of the Bethe-Salpeter equation. In particular, the experimental peak position of the exciton is accurately reproduced.

Ultrafast nonequilibrium dynamics of rotons in superfluid helium.

Short-time dynamics of superfluids far from equilibrium remains largely unknown, despite its importance for key processes in these systems. Here, we describe a method for locally perturbing the density of superfluid helium via the excitation of roton pairs with ultrashort laser pulses. By measuring the time dependence of this perturbation, we track the nonequilibrium dynamics of the two-roton states on femtosecond and picosecond timescales. Our results reveal an ultrafast equilibration of roton pairs as they thermalize with the colder equilibrium quasiparticle gas. Future applications of this technique to different temperature and pressure regimes, in various superfluids, will enable to probe rapid nucleation and decay processes, as well as metastable Bose-Einstein condensates of rotons and roton pairs.

Ultrafast many-body bright-dark exciton transition in anatase TiO2.

The momentum-forbidden dark excitons can have a pivotal role in quantum information processing, Bose-Einstein condensation, and light-energy harvesting. Anatase TiO2 with an indirect band gap is a prototypical platform to study bright to momentum-forbidden dark exciton transition. Here, we examine, by GW plus the real-time Bethe-Salpeter equation combined with the nonadiabatic molecular dynamics (GW + rtBSE-NAMD), the many-body transition that occurs within 100 fs from the optically excited bright to the strongly bound momentum-forbidden dark excitons in anatase TiO2. Comparing with the single-particle picture in which the exciton transition is considered to occur through electron-phonon scattering, within the GW + rtBSE-NAMD framework, the many-body electron-hole Coulomb interaction activates additional exciton relaxation channels to notably accelerate the exciton transition in competition with other radiative and nonradiative processes. The existence of dark excitons and ultrafast bright-dark exciton transitions sheds insights into applications of anatase TiO2 in optoelectronic devices and light-energy harvesting as well as the formation process of dark excitons in semiconductors.

A deep transfer learning-based protocol accelerates full quantum mechanics calculation of protein.

Effective full quantum mechanics (FQM) calculation of protein remains a grand challenge and of great interest in computational biology with substantial applications in drug discovery, protein dynamic simulation and protein folding. However, the huge computational complexity of the existing QM methods impends their applications in large systems. Here, we design a transfer-learning-based deep learning (TDL) protocol for effective FQM calculations (TDL-FQM) on proteins. By incorporating a transfer-learning algorithm into deep neural network (DNN), the TDL-FQM protocol is capable of performing calculations at any given accuracy using models trained from small datasets with high-precision and knowledge learned from large amount of low-level calculations. The high-level double-hybrid DFT functional and high-level quality of basis set is used in this work as a case study to evaluate the performance of TDL-FQM, where the selected 15 proteins are predicted to have a mean absolute error of 0.01 kcal/mol/atom for potential energy and an average root mean square error of 1.47 kcal/mol/$ {\rm A^{^{ \!\!\!o}}} $ for atomic forces. The proposed TDL-FQM approach accelerates the FQM calculation more than thirty thousand times faster in average and presents more significant benefits in efficiency as the size of protein increases. The ability to learn knowledge from one task to solve related problems demonstrates that the proposed TDL-FQM overcomes the limitation of standard DNN and has a strong power to predict proteins with high precision, which solves the challenge of high precision prediction in large chemical and biological systems.

Molecular Insights into Chemical Reactions at Aqueous Aerosol Interfaces.

Atmospheric aerosols facilitate reactions between ambient gases and dissolved species. Here, we review our efforts to interrogate the uptake of these gases and the mechanisms of their reactions both theoretically and experimentally. We highlight the fascinating behavior of N2O5 in solutions ranging from pure water to complex mixtures, chosen because its aerosol-mediated reactions significantly impact global ozone, hydroxyl, and methane concentrations. As a hydrophobic, weakly soluble, and highly reactive species, N2O5 is a sensitive probe of the chemical and physical properties of aerosol interfaces. We employ contemporary theory to disentangle the fate of N2O5 as it approaches pure and salty water, starting with adsorption and ending with hydrolysis to HNO3, chlorination to ClNO2, or evaporation. Flow reactor and gas-liquid scattering experiments probe even greater complexity as added ions, organic molecules, and surfactants alter the interfacial composition and reaction rates. Together, we reveal a new perspective on multiphase chemistry in the atmosphere.

Many-body effects in the X-ray absorption spectra of liquid water.

SignificanceIn X-ray absorption spectroscopy, an electron-hole excitation probes the local atomic environment. The interpretation of the spectra requires challenging theoretical calculations, particularly in a system like liquid water, where quantum many-body effects and molecular disorder play an important role. Recent advances in theory and simulation make possible new calculations that are in good agreement with experiment, without recourse to commonly adopted approximations. Based on these calculations, the three features observed in the experimental spectra are unambiguously attributed to excitonic effects with different characteristic correlation lengths, which are distinctively affected by perturbations of the underlying H-bond structure induced by temperature changes and/or by isotopic substitution. The emerging picture of the water structure is fully consistent with the conventional tetrahedral model.

Chirality-Dependent Dynamic Evolution for Trions in Monolayer WS2.

Monolayer transition metal dichalcogenides exhibit valley-dependent excitonic characters with a large binding energy, acting as the building block for future optoelectronic functionalities. Herein, combined with pump-probe ultrafast transient transmission spectroscopy and theoretical simulations, we reveal the chirality-dependent trion dynamics in h-BN encapsulated monolayer tungsten disulfide. By resonantly pumping trions in a single valley and monitoring their temporal evolution, we identify the temperature-dependent competition between two relaxation channels driven by chirality-dependent scattering processes. At room temperature, the phonon-assisted upconversion process predominates, converting excited trions to excitons within the same valley on a sub-picosecond (ps) time scale. As temperature decreases, this process becomes less efficient, while alternative channels, notably valley depolarization process for trions, assume importance, leading to an increase of trion density in the unpumped valley within a ps time scale. Our time-resolved valley-contrast results provide a comprehensive insight into trion dynamics in 2D materials, thereby advancing the development of novel valleytronic devices.

Ultrafast Coherent Exciton Couplings and Many-Body Interactions in Monolayer WS2.

Transition metal dichalcogenides (TMDs) are quantum confined systems with interesting optoelectronic properties, governed by Coulomb interactions in the monolayer (1L) limit, where strongly bound excitons provide a sensitive probe for many-body interactions. Here, we use two-dimensional electronic spectroscopy (2DES) to investigate many-body interactions and their dynamics in 1L-WS2 at room temperature and with sub-10 fs time resolution. Our data reveal coherent interactions between the strongly detuned A and B exciton states in 1L-WS2. Pronounced ultrafast oscillations of the transient optical response of the B exciton are the signature of a coherent 50 meV coupling and coherent population oscillations between the two exciton states. Supported by microscopic semiconductor Bloch equation simulations, these coherent dynamics are rationalized in terms of Dexter-like interactions. Our work sheds light on the role of coherent exciton couplings and many-body interactions in the ultrafast temporal evolution of spin and valley states in TMDs.

Acoustic manipulation of multi-body structures and dynamics.

Sound can exert forces on objects of any material and shape. This has made the contactless manipulation of objects by intense ultrasound a fascinating area of research with wide-ranging applications. While much is understood for acoustic forcing of individual objects, sound-mediated interactions among multiple objects at close range gives rise to a rich set of structures and dynamics that are less explored and have been emerging as a frontier for research. We introduce the basic mechanisms giving rise to sound-mediated interactions among rigid as well as deformable particles, focusing on the regime where the particles' size and spacing are much smaller than the sound wavelength. The interplay of secondary acoustic scattering, Bjerknes forces, and micro-streaming is discussed and the role of particle shape is highlighted. Furthermore, we present recent advances in characterizing non-conservative and non-pairwise additive contributions to the particle interactions, along with instabilities and active fluctuations. These excitations emerge at sufficiently strong sound energy density and can act as an effective temperature in otherwise athermal systems.

Pseudo-fermion functional renormalization group for spin models.

For decades, frustrated quantum magnets have been a seed for scientific progress and innovation in condensed matter. As much as the numerical tools for low-dimensional quantum magnetism have thrived and improved in recent years due to breakthroughs inspired by quantum information and quantum computation, higher-dimensional quantum magnetism can be considered as the final frontier, where strong quantum entanglement, multiple ordering channels, and manifold ways of paramagnetism culminate. At the same time, efforts in crystal synthesis have induced a significant increase in the number of tangible frustrated magnets which are generically three-dimensional in nature, creating an urgent need for quantitative theoretical modeling. We review the pseudo-fermion (PF) and pseudo-Majorana (PM) functional renormalization group (FRG) and their specific ability to address higher-dimensional frustrated quantum magnetism. First developed more than a decade ago, the PFFRG interprets a Heisenberg model Hamiltonian in terms of Abrikosov pseudofermions, which is then treated in a diagrammatic resummation scheme formulated as a renormalization group flow ofm-particle pseudofermion vertices. The article reviews the state of the art of PFFRG and PMFRG and discusses their application to exemplary domains of frustrated magnetism, but most importantly, it makes the algorithmic and implementation details of these methods accessible to everyone. By thus lowering the entry barrier to their application, we hope that this review will contribute towards establishing PFFRG and PMFRG as the numerical methods for addressing frustrated quantum magnetism in higher spatial dimensions.

Electronic structure of the strongly correlated electron system plutonium hexaboride: A study from single-particle approximations and many-body calculations.

The electronic structure of the strongly correlated electron system plutonium hexaboride is studied by using single-particle approximations and a many-body approach. Imaginary components of impurity Green's functions show that 5fj=5/2 and 5fj=7/2 manifolds are in conducting and insulating regimes, respectively. Quasi-particle weights and their ratio suggest that the intermediate coupling mechanism is applicable for Pu 5f electrons, and PuB6 might be in the orbital-selective localized state. The weighted summation of occupation probabilities yields the interconfiguration fluctuation and average occupation number of 5f electrons n5f ~ 5.101. The interplay of 5f-5f correlation, spin-orbit coupling, Hund's exchange interaction, many-body transition of 5f configurations, and final state effects might be responsible for the quasiparticle multiplets in electronic spectrum functions. Prominent characters in the density of state, such as the coexistence of atomic multiplet peaks in the vicinity of the Fermi level and broad Hubbard bands in the high-lying regime, suggest that PuB6 could be identified as a Racah material. Finally, the quasiparticle band structure is also presented.

Many-Body Effects in Aqueous Systems: Synergies Between Interaction Analysis Techniques and Force Field Development.

Interaction analysis techniques, including the many-body expansion (MBE), symmetry-adapted perturbation theory, and energy decomposition analysis, allow for an intuitive understanding of complex molecular interactions. We review these methods by first providing a historical context for the study of many-body interactions and discussing how nonadditivities emerge from Hamiltonians containing strictly pairwise-additive interactions. We then elaborate on the synergy between these interaction analysis techniques and the development of advanced force fields aimed at accurately reproducing the Born-Oppenheimer potential energy surface. In particular, we focus on ab initio-based force fields that aim to explicitly reproduce many-body terms and are fitted to high-level electronic structure results. These force fields generally incorporate many-body effects through (a) parameterization of distributed multipoles, (b) explicit fitting of the MBE, (c) inclusion of many-atom features in a neural network, and (d) coarse-graining of many-body terms into an effective two-body term. We also discuss the emerging use of the MBE to improve the accuracy and speed of ab initio molecular dynamics.

The Optical Signatures of Stochastic Processes in Many-Body Exciton Scattering.

We review our recent quantum stochastic model for spectroscopic lineshapes in the presence of a coevolving and nonstationary background population of excitations. Starting from a field theory description for interacting bosonic excitons, we derive a reduced model whereby optical excitons are coupled to an incoherent background via scattering as mediated by their screened Coulomb coupling. The Heisenberg equations of motion for the optical excitons are then driven by an auxiliary stochastic population variable, which we take to be the solution of an Ornstein-Uhlenbeck process. Here, we present an overview of the theoretical techniques we have developed as applied to predicting coherent nonlinear spectroscopic signals. We show how direct (Coulomb) and exchange coupling to the bath give rise to distinct spectral signatures and discuss mathematical limits on inverting spectral signatures to extract the background density of states.

Ising-like Model Hasn't Yet Said its Last Word: Exact and Mean-Field Investigations of 2, 3 and 4-Body Interactions in 1D Ising Chain of Binuclear Spin-Crossover Solids.

We investigate the static properties of a new class of 1D Ising-like Hamiltonian for binuclear spin-crossover materials accounting for two-, three-, and four-body short-range interactions between binuclear units of spins [[EQUATION]] and [[EQUATION]]. The following 2-, 3- , and 4-body [[EQUATION]], [[EQUATION]], and [[EQUATION]] terms are considered, in addition to intra-binuclear interactions, such as effective ligand-field energy and exchange-like coupling. An exact treatment is carried out within the frame of the transfer matrix method, leading to a [[EQUATION]] matrix from which, we obtained the thermal evolution of the thermodynamic quantities. Several situations of model parameter values were tested, among which that of competing intra- and inter-molecular interactions, leading to the occurrence of (i) one-step spin transition, (ii) two-, three-, and four-step transitions, obtained with a reasonable number of parameters. To reproduce first-order phase transitions, we accounted for inter-chains interactions, treated in the mean-field approach. Hysteretic multi-step transitions, recalling experimental observations, are then achieved. Overall, the present model not only suggests new landscapes of interaction configurations between SCO molecules but also opens new avenues to tackle the complex behaviors often observed in the properties of SCO materials.

Evidence of ideal excitonic insulator in bulk MoS2 under pressure.

Spontaneous condensation of excitons is a long-sought phenomenon analogous to the condensation of Cooper pairs in a superconductor. It is expected to occur in a semiconductor at thermodynamic equilibrium if the binding energy of the excitons-electron (e) and hole (h) pairs interacting by Coulomb force-overcomes the band gap, giving rise to a new phase: the "excitonic insulator" (EI). Transition metal dichalcogenides are excellent candidates for the EI realization because of reduced Coulomb screening, and indeed a structural phase transition was observed in few-layer systems. However, previous work could not disentangle to which extent the origin of the transition was in the formation of bound excitons or in the softening of a phonon. Here we focus on bulk [Formula: see text] and demonstrate theoretically that at high pressure it is prone to the condensation of genuine excitons of finite momentum, whereas the phonon dispersion remains regular. Starting from first-principles many-body perturbation theory, we also predict that the self-consistent electronic charge density of the EI sustains an out-of-plane permanent electric dipole moment with an antiferroelectric texture in the layer plane: At the onset of the EI phase, those optical phonons that share the exciton momentum provide a unique Raman fingerprint for the EI formation. Finally, we identify such fingerprint in a Raman feature that was previously observed experimentally, thus providing direct spectroscopic confirmation of an ideal excitonic insulator phase in bulk [Formula: see text] above 30 GPa.

Phonon-Mediated Quasiparticle Lifetime Renormalizations in Few-Layer Hexagonal Boron Nitride.

Understanding the collective behavior of the quasiparticles in solid-state systems underpins the field of nonvolatile electronics, including the opportunity to control many-body effects for well-desired physical phenomena and their applications. Hexagonal boron nitride (hBN) is a wide-energy-bandgap semiconductor, showing immense potential as a platform for low-dimensional device heterostructures. It is an inert dielectric used for gated devices, having a negligible orbital hybridization when placed in contact with other systems. Despite its inertness, we discover a large electron mass enhancement in few-layer hBN affecting the lifetime of the π-band states. We show that the renormalization is phonon-mediated and consistent with both single- and multiple-phonon scattering events. Our findings thus unveil a so-far unknown many-body state in a wide-bandgap insulator, having important implications for devices using hBN as one of their building blocks.

Trion Formation Resolves Observed Peak Shifts in the Optical Spectra of Transition-Metal Dichalcogenides.

Monolayer transition-metal dichalcogenides (ML-TMDs) have the potential to unlock novel photonic and chemical technologies if their optoelectronic properties can be understood and controlled. Yet, recent work has offered contradictory explanations for how TMD absorption spectra change with carrier concentration, fluence, and time. Here, we test our hypothesis that the large broadening and shifting of the strong band-edge features observed in optical spectra arise from the formation of negative trions. We do this by fitting an ab initio based, many-body model to our experimental electrochemical data. Our approach provides an excellent, global description of the potential-dependent linear absorption data. We further leverage our model to demonstrate that trion formation explains the nonmonotonic potential dependence of the transient absorption spectra, including through photoinduced derivative line shapes for the trion peak. Our results motivate the continued development of theoretical methods to describe cutting-edge experiments in a physically transparent way.

Excitonic Effects in Energy-Loss Spectra of Freestanding Graphene.

In this work, we perform electron energy-loss spectroscopy (EELS) of freestanding graphene with high energy and momentum resolution to disentangle the quasielastic scattering from the excitation gap of Dirac electrons close to the optical limit. We show the importance of many-body effects on electronic excitations at finite transferred momentum by comparing measured EELS to ab initio calculations at increasing levels of theory. Quasi-particle corrections and excitonic effects are addressed within the GW approximation and the Bethe-Salpeter equation, respectively. Both effects are essential in the description of the EEL spectra to obtain a quantitative agreement with experiments, with the position, dispersion, and shape of both the excitation gap and the π plasmon being significantly affected by excitonic effects.

Rapid Suppression of Quantum Many-Body Magnetic Exciton in Doped van der Waals Antiferromagnet (Ni,Cd)PS3.

The unique discovery of the magnetic exciton in van der Waals antiferromagnet NiPS3 arises between two quantum many-body states of a Zhang-Rice singlet excited state and a Zhang-Rice triplet ground state. Simultaneously, the spectral width of photoluminescence originating from this exciton is exceedingly narrow as 0.4 meV. These extraordinary properties, including the extreme coherence of the magnetic exciton in NiPS3, beg many questions. We studied doping effects using Ni1-xCdxPS3 using two experimental techniques and theoretical studies. Our experimental results show that the magnetic exciton is drastically suppressed upon a few % Cd doping. All this happens while the width of the exciton only gradually increases and the antiferromagnetic ground state is robust. These results highlight the lattice uniformity's hidden importance as a prerequisite for coherent magnetic exciton. Finally, an exciting scenario emerges: the broken charge transfer forbids the otherwise uniform formation of the coherent magnetic exciton in (Ni,Cd)PS3.