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This chapter provides readers who are encountering full quantum effects for the first time, with a comprehensive conceptual understanding of the condensed matter physics problems, and prepares them for further exploration of the intrinsic connection between specific macroscopic phenomena and their underlying microscopic mechanisms. It can introduce, in light-element systems, significant nuclear quantum effects (NQEs) and nonadiabatic effects, including quantum tunneling, quantum fluctuations, zero-point energy, and electron–phonon coupling. These effects have significant influence on the atomic structure (e.g., liquid state of helium), electronic structure (e.g., electron bandgap), thermodynamics (e.g., ultra-low thermal conductivity), optical properties (e.g., absorption spectra and formation of polaron), and quantum paraelectricity. As a prominent example, the superfluid and supersolid in helium systems originate from the NQEs. And nonadiabatic effects affect atomic vibrations (e.g., shift of phonon frequency) and collisions, leading to the breaking and reorganization of chemical bonds. These processes significantly affect ultrafast electron transfer (e.g., novel transfer rate dependence outside Fermi’s golden rule), electron–phonon coupling strength, the formation of charge density waves, phase transition dynamics, Berry phase, and superconductivity.
The extreme heat fluxes characteristic of hypersonic flows significantly limit the flight envelope of hypersonic vehicles. The role of hydrodynamic instability and the onset of laminar-to-turbulent boundary layer transition is of notable importance. The effect of streaks on the suppression of planar (second Mack mode) instabilities has been previously investigated, but a potentially passive and non-intrusive control method has not been established yet. Recent work shows that streaks can be generated through a spanwise variation in surface temperature. This method exploits the aerothermodynamic characteristics of the flow, and therefore promises to be robust. This work uses direct numerical simulations to determine and quantify the effectiveness of this novel control method in the suppression of second Mack mode instability for a hypersonic boundary layer over a flat plate. The computational analyses cover a range of Mach numbers, 4.8–6, and wall temperature ratios representative of both wind tunnel testing and flight scenarios. Among the range of configurations investigated, the energy of the second Mack mode is reduced by up to approximately 60 % by the steady streaks. The streak wavelength parameter plays a significant role in the stabilisation benefits. For a Mach 6 configuration, for the most linearly amplified second Mack mode disturbance frequency, nearly optimum performance is achieved for a spanwise wavelength of approximately 8–10 times the local boundary layer thickness. These findings open new avenues for controlling hypersonic boundary layers and offer valuable guidance for future experimental campaigns aimed at validating this novel control strategy.
This chapter delves into theoretical methods of electronic structure, which is the basis to simulate a real condensed matter system accurately at the quantum-mechanical level. It begins with an overview of the history of full quantum theory, which describes the quantum properties of nucleus, electron and their quantum coupling. Beyond the Born–Oppenheimer approximation, Born–Huang expansion is introduced which expands the system as a sum over electron–nuclear wavefunction products. It is a rigorous approach describing electron–phonon coupling and is believed to become the dominant paradigm in condensed matter physics with the rapid improvement of simulation and high-resolved experimental techniques. History, theoretical framework, and challenges of the mainstream electronic structure calculation methods are introduced. These include wavefunction method (Hartree method, Hartree–Fock method, and post-Hartree–Fock method), density functional theory (DFT), and Quantum Monte Carlo Method (QMC). The accuracy of post-Hartree–Fock methods (consider dynamical correlation of electron) makes them remain important while DFT is the most common method in physics, chemistry and material, being important foundation of full-quantum calculation. The impact of QMC keeps increasing in computational physics due to its adaptation to supercomputers. Then, the method for excited electronic state calculation is introduced, which is also needed in full quantum calculation. The GW Method is recommended because it can treat the quasiparticle–electron excitation properties accurately. Finally, the chapter introduces current realizations of electronic-structure calculation and their challenges (e.g., balance between accuracy and efficiency). It discusses key concepts such as basis set, pseudopotential, and boundary condition. The associated programs are summarized.
A key goal of condensed matter physics is to describe the properties of a quantum many-body interacting system in an accurate manner. The Born–Oppenheimer (BO) approximation, which was proposed right after the establishment of the Schrödinger Equation, has been the foundation of researches on polyatomic systems including condensed matter for about 100 years. For theoreticians, it is the starting point for the vast majority of simulations; for experimentalists, it is the theoretical tool on which most researchers rely when interpreting observations. Based on the BO approximation, the electronic structures of condensed matter can be described using a specific spatial configuration of the nuclei. Upon this, the vibrations of the lattice were treated using the concept of phonon. The electron–phonon interactions exist, and they can be addressed in terms of the many-body perturbation theory. In recent years, however, there has been a growing interest in studies of condensed matter beyond this scenario, driven by advancements in high-precision experiments and theoretical simulations. This situation prompts the studies of full quantum effects (FQEs), including those related to the nuclear quantum effects beyond the harmonic approximation and those related to the nonadiabatic effects. The Born–Huang expansion forms the basis of these studies. Various experiments introduced here were pushed to the limits of ultrahigh resolution in order to highlight observational details reflecting FQEs rather than the classical ones. Using water, the most ubiquitous substance on earth as an example, we show that FQEs can, both qualitatively and quantitatively, affect the water hydrogen bond structure, energy, and dynamics. Although FQEs are found in the past mostly prominent under extreme condition (e.g., low temperature, ultrafast timescale, single-molecule level) or in the elementary process (e.g., electron excitation, proton transfer, vibration), the unveiled law is expected to extend to the wide condensed physical and chemistry systems. In these systems, some of the basic interactions in the Schrödinger Equation, such as electron–electron and electron–nucleus interactions as well as nucleus character energy, are comparable to each other, which makes quantization of nuclei indispensable for accurate simulations and measurements. As such, simulation methods for nuclear quantum dynamics, nonadiabatic dynamics with electron excitation under external fields, as well as combination of the two, are the particular challenge in developing computational methods for FQE research. Experiments, in the meantime, are moving in a direction that combines ultrafast laser technology with traditional spectroscopy, while characterization techniques and the material quality need optimization in special environments to allow effective observations of FQE at the single-atom or single-bond level.
We consider the response of a flexibly mounted square prism placed in inertial-viscoelastic fluid flow with one degree-of-freedom in the cross-flow direction. Under these flow conditions, both inertia and elastic effects are significant. We model the system numerically using a two-way coupling scheme to simulate the interaction between the fluid and the spring–mass system at a Reynolds number of $\textit{Re}=200$ for two mass ratios of $m^* = 2$ and 20, and a Weissenberg number of $\textit{Wi}=2$, across a range of reduced velocities. We demonstrate that introducing fluid elasticity suppresses vortex-induced vibrations of square prisms, consistent with prior findings for circular bluff bodies. However, we find that fluid elasticity amplifies the galloping response in comparison with the response in a Newtonian fluid, leading to larger oscillation amplitudes and the onset of galloping at lower reduced velocities. The predicted enhancement in galloping is significant, particularly at low mass ratios, where no galloping is observed over the wide reduced velocity range tested for Newtonian fluids. We show that this enhancement of galloping is likely the result of the observation that the addition of viscoelasticity increases the magnitude of the rate of change of the transverse flow-induced force on the prism with increasing angle of attack of the incoming flow.
This chapter focuses on research progress related to full quantum effects in dense hydrogen, hydride compounds, and proton transport through 2D materials and bulk materials where hydrogen does not dominate in content. For dense hydrogen, this chapter describes nuclear quantum effects in high-pressure phase diagram, phase transition, and physical property. For the most common hydride compound, water, this chapter introduces nuclear quantum effects in water hydrogen bond property, water phase diagram, and physical and chemical property of confined water and ice. For other hydride compound, this chapter introduces full quantum effects in hydride superconductivity and nonlinear optical property of mineral hydride. These studies reveal that, full quantum effect not only has significant contribution to existing properties, such as hydrogen bond strength and phase diagram boundary probed by isotope substitution, but also causes novel states and properties, such as room temperature, high-pressure superconductivity of hydrides (e.g., sulfur hydride) and liquid forms of metallic and superconducting hydrogen. After these, this chapter introduces theory of proton tunneling rate, which is important from physical to life sciences. Theory of proton transport in perovskite-type oxides is also illustrated as typical example of nuclear quantum effects on hydrogen conduction in bulk materials. Finally, the chapter introduces work demonstrating importance of proton tunneling in DNA mutation.
This chapter explores, for condensed matter formed by other elements, the novel physical and chemical properties that are dominated by full quantum effects. This includes elementary substances including relatively light elements (e.g., helium (He), lithium (Li), carbon (C), and boron (B)) as well as relatively heavy elements (e.g., oxygen (O) and silicon (Si)), and their compounds. The objects studied include liquid and solid helium, lithium bulk metal and clusters, bulk boron, borophene, boron nitride nanotubes, hexagonal boron nitride, magnesium diboride, diamond, graphene, carbon atoms in organic molecules, strontium titanate, barium ferrite, silicon semiconductors, etc. The related physical and chemical properties include superfluidity, supersolidity, elastic or plastic deformation, heat capacity, high-pressure phase diagram, bonding lengths, diffusion, crystal structure, electron–phonon coupling, bandgap renormalization, thermal expansion coefficient, thermal conductivity, phonon frequency distribution, superconducting temperature and light absorption, etc. Through a variety of fruitful aspects readers would overview the situations where full quantum effect is pronounced and even critical.
This chapter explores the significant influence of full quantum effects on chemical reactions, surpassing the framework of classical transition-state theory (TST). For light element systems (e.g., H2, O2), quantum tunneling, vibration, and electron–nucleus quantum coupling have decisive impacts on the reaction process. Advancements in reaction rate theory incorporate tunneling and zero-point energy into TST, while the field waits for the development of a more comprehensive TST that precisely treats full quantum effects. Nuclear quantum effect is critical in hydrogen dynamics at room temperatures (even above 500 K), ultracold reactions, penning discharge, nonclassical product formation in organic reactions, performance improvement in electrolysis utilizing kinetic isotope effects (e.g., in aqueous batteries), and biochemical reactions. Quantum tunneling is likely to facilitate the origin of life at its early stage by increasing the rate of forming organic molecules. Nonadiabatic effects (NAEs) manifest in altering electronic eigenstate population (e.g., relaxation dynamics) and dynamic nuclear transfer between split potential energy surfaces (e.g., chlorine–hydrogen collision, water photodissociation), demonstrated or indicated by experiment or theoretical calculation.
We perform direct numerical simulations of continuously growing broadband surface waves forced by a turbulent atmospheric boundary layer coupled with a developing underwater current. We resolve and analyse the multiscale space–time evolution of the waves by considering the wave spectrum in frequency and wavenumber space and describe the kinematics of nonlinear gravity–capillary waves under a current initially described by a viscous boundary layer and transitioning to turbulence at later times under the wind-wave forcing. The wave speed experiences a scale-dependent Doppler shift, with shorter waves shifted by currents closer to the surface, in agreement with the framework from Stewart & Joy (1974 Deep Sea Res. Oceanogr. Abstracts 21(12), 1039–1049). At low wave slopes, the wave energy concentrates along the linear dispersion relation. When the wave slope is high enough, we observe wave energy located in multiple branches associated with nonlinear bound harmonics travelling at the speed of a carrier mode. These nonlinear branches are well described by a generalized nonlinear dispersion relation that links each harmonic to the effective velocity of the carrier mode to which they are bound, and are found to be Doppler shifted with the carrier mode. The generalized Doppler-shifted nonlinear dispersion relation remains valid as the underwater current becomes turbulent, and the depth-varying mean current profile can be systematically reconstructed from the measured phase velocities from waves at different scales.
We investigate thermal boundary layer (BL) asymmetry in turbulent Rayleigh–Bénard convection (RBC) under both spherical and annular geometries using different BL theories. Unlike planar RBC, the spherical and annular configurations exhibit asymmetric thermal BLs near the inner and outer boundaries due to boundary curvature and non-uniform radial gravity. We generalise three BL frameworks – the Prandtl–Blasius BL model, the steady free-convective model and the fluctuating BL model – and apply them to both geometries. Direct numerical simulations (DNSs), based on the Oberbeck–Boussinesq equations, are performed in three-dimensional spherical RBC and three-dimensional annular RBC for various radius ratios ($\eta$), gravity profiles and also Prandtl numbers ($ \textit{Pr}$), to compare with the predictions of the extended BL models. We find that the BL asymmetries predicted by both the extended steady free-convective BL and the fluctuating BL agree well with DNS results, with the fluctuating BL model providing the best agreement for the mean temperature profiles. A force-balance analysis further shows that this better performance is consistent with the DNS observation that, in the wall-normal direction within the thermal BL, buoyancy is balanced primarily by the pressure-gradient force. This is consistent with the assumption underlying the steady free-convective and fluctuating BL models. Moreover, the fluctuating BL model explicitly accounts for the contribution of turbulent fluctuations to the heat flux, which further improves its agreement with the DNS mean temperature profiles. We derive analytical expressions for the bulk temperature and the thermal BL thickness ratio as functions of the radius ratio and gravity profile across different Prandtl-number regimes. These expressions are obtained by integrating the similarity thermal equation for both the inner and outer BLs using an approximate similarity streamfunction, and by closing the solutions through a heat-flux matching condition. The resulting leading-order expressions obtained from both the steady free-convective and fluctuating BL models are shown to be the same, and they agree well with DNS data. This analytical result provides a robust and practical tool for quantifying BL asymmetry in curved RBC systems.
We consider free-surface flows driven by turbulence beneath the surface, particularly the strong free-surface turbulence (FST) regime, characterised by large Froude number ${\textit {Fr}}^2_T=\varepsilon /u_{\textit{rms}} {g}\,\gtrsim 0.1$. We study the surface layer, where air and water are highly mixed and turbulence modelling is challenging. We develop a definition of the surface-layer thickness $\delta _s$ based on the vertical derivative of intermittency $\gamma$ at the mean free surface $\bar {\eta }$, which, unlike previous definitions, is independent of the tail behaviour of $\gamma$. From direct numerical simulation (DNS) of statistically stationary, horizontally homogeneous strong FST, we show that scaling by $z^* = (z-\bar {\eta })/\delta _s$ collapses $\gamma$ across a wide range of ${\textit {Fr}}^2_T\in [0.03,0.3]$. The distribution more closely follows logistic rather than Gaussian behaviour. From the near-surface turbulence obtained from DNS, we make two general observations. First, we show that for strong FST there is minimal direct effect of the free surface on the isotropy, turbulence kinetic energy $\tilde {k}$ or dissipation rate $\varepsilon$ beneath the surface layer ($z^*\lt -0.5$). Instead, turbulence is only indirectly affected through the flux of kinetic energy into the surface layer. Second, we show that many relevant metrics within the surface layer ($z^*\in [-0.5, 0.5]$) collapse when appropriately scaled by $u_{\textit{rms}}^2=2\tilde {k}/3$ and $\varepsilon$ measured at $z^*=-0.5$. These observations suggest the possibility of a turbulence closure model which avoids direct modelling of $\tilde {k}$ and $\varepsilon$ in the surface layer. Towards this, we show that, across a wide range of ${\textit {Fr}}_T^2$, surface-layer thickness can be predicted by $\delta _s \approx 11.1 \,u_{\textit{rms}}^2 {g}^{-1}$ and energy flux into the surface layer by $W \approx 0.41 \,\varepsilon \delta _s$.
This work employs structured input–output analysis (SIOA) augmented by an eddy viscosity model (SIOA-e) to investigate turbulent flows over rigid and compliant walls. The SIOA-e framework demonstrates the capability in identifying both streamwise and spanwise dominant characteristic wavelengths for rigid wall turbulence. For compliant walls, the SIOA-e method predicts optimal compliant wall parameters associated with positive damping coefficients when minimizing input–output gain for near-wall cycle and very large-scale motions, respectively. The reduction of input–output gain due to the compliant wall is achieved by wall displacement resembling blowing and suction opposite to the wall-normal velocity of dominant streamwise vortices. However, optimized compliant wall parameters based on specific wavenumber–frequency combinations may amplify flow structures for other wavenumber–frequency pairs, potentially leading to an overall drag increase. For example, compliant wall parameters tuned for suppressing large-scale structures can affect both large- and small-scale structures. We also employ input–output analysis to predict convective velocity of wall displacement and pressure for turbulent flow over the compliant wall, and the predicted convective velocity of wall displacement is 0.53 times centreline velocity, which aligns well with recent experimental measurements.