Abstract The advantages of the direct combustion of agricultural biomass for power generation are restricted due to the drawbacks of this biomass and the deep peak shaving trend. Hydrothermal carbonization can improve the physical and thermochemical properties of raw materials. Corn stalk samples were selected as the research object in this study. Corn stalk hydrochars were prepared with reaction pressures of 0–3 MPa, reaction temperatures of 160–240 °C, and residence times of 1–10 h. The effects of the process parameters on the physicochemical properties of hydrochar and on the removal of alkali and alkaline earth metals (AAEMs) were studied by measuring the hydrochar mass, energy yield, product composition, morphology, as well as the removal efficiency of AAEMs. The results indicated that the corn stalk hydrochar had higher mass and energy yields than the raw corn stalk. X‐ray diffraction showed that the carbon content in the hydrochar was greater than that in raw corn stalk. Scanning electron microscopy showed that the reaction temperature played a more significant role in the hydrothermal carbonization process than the reaction pressure and residence time.
Gradient corrections to the local spin density (LSD) approximation for the exchange-correlation energy are making density functional theory as useful in quantum chemistry as it is in solid-state physics. But which of the many gradient-corrected density functionals should be preferred a priori? We make a graphical comparison of the gradient dependencies of some popular approximations, discussing the exact formal conditions which each obeys and identifying which conditions seem most important. For the exchange energy, there is little formal or practical reason to choose among the Perdew-Wang 86, Becke 88, or Perdew-Wang 91 functionals. But, for the correlation energy, the best formal properties are displayed by the nonempirical PW91 correlation functional. Furthermore, the real-space foundation of PW91 yields an insight into the character of the gradient expansion which suggests that PW91 should work especially well for solids. Indeed, while improving dissociation energies over LSD, PW91 remains the most “local” of the gradient-corrected exchange-correlation functionals and, thus, the least likely to overcorrect the subtle errors of LSD for solids. To show that our analysis of spin-unpolarized functionals is sufficient, we also compute spin-polarization energies for atoms, finding PW91 values only slightly more negative than LSD values. © 1996 John Wiley & Sons, Inc.
Density functional theory (DFT) is a widespread and effective tool in electronic structure calculations for ground-state electron systems. Its success has prompted exploration into the use of DFT for non-collective excited states. The delta self-consistent field ($Δ$SCF) method allows for the extension of DFT to excited-state energies by restricting the Kohn-Sham orbital occupations, producing an excited-state electron density, and then computing its energy. In this paper, we examine the performance of the LSDA, PBE generalized-gradient approximation (GGA), and SCAN/r2SCAN meta-GGA for the excitation energies of several important systems. We consider the energies of atoms with atomic number 1-18. For the hydrogen atom, where we use the exact electron density and have no multiplet splitting, we find significant improvement up the ladder from LSDA to PBE to SCAN. For the uniform gas, we find an effective mass different from the bare mass only with r2SCAN. We split the case of multi-electron atoms into non-aufbau excitations, where the highest-energy electron is excited to the lowest state in the next nl subshell (where accuracy is least limited by available basis sets), and spin-flip excitations, where the spin of an electorn is flipped, leading to a higher-energy state of the same nl configuration. We find reasonably accurate approximate excitation energies, except for the spin-flip cases where the auxiliary non-interacting wavefunction of a non-Hund's-rule spin state is not well-described by a single determinant.
Although the density-gradient expansion for the noninteracting fermion kinetic energy is known through sixth order, numerical tests and applications of it have so far only been made through fourth order because its sixth-order term (${\mathrm{T}}_{6}$) diverges in the exponentially decaying tail of the electron density for a finite system. We show that ${\mathrm{T}}_{6}$ provides a useful correction to the density functional ${\mathrm{T}}_{0}$+${\mathrm{T}}_{2}$+${\mathrm{T}}_{4}$ for a problem in which the density n(r) is everywhere bounded from below: the formation energy of a monovacancy in jellium. Thus the sixth-order expansion may be useful in condensed-matter physics or perhaps more generally via convergent resummation. We also suggest that the most important terms of the series may be those involving |\ensuremath{\nabla}n${\mathrm{|}}^{2}$ and ${\mathrm{\ensuremath{\nabla}}}^{2}$n, but no other derivative.
By analogy with the change-in-self-consistent-field ($\ensuremath{\Delta}\mathrm{SCF}$) method of atomic physics, the work function of a metal surface is computed as the difference between the total energy of the system in its final state, where one electron is missing from the metal and removed to a large distance from the surface, and its initial state, where the metal is charge neutral. Our $\ensuremath{\Delta}\mathrm{SCF}$ expression is a generalization of one given by Lang and Kohn, who assumed the electron density profile to be that of a jellium surface. The $\ensuremath{\Delta}\mathrm{SCF}$ expression also reduces in the appropriate limit to an expression derived by Mahan and Schaich. We show that the $\ensuremath{\Delta}\mathrm{SCF}$ expression is much less profile-sensitive than other exact expressions for the work function and is therefore well suited for use with approximate profiles. We apply our "variational self-consistent" profiles (more realistic than jellium profiles) to evaluate the $\ensuremath{\Delta}\mathrm{SCF}$ work function for a few selected surfaces of simple metals, among them the three low-index faces of Al, for which agreement with experiment is found to be good.
Kohn-Sham density functional theory (DFT) is a widely-used electronic structure theory for materials as well as molecules. DFT is needed especially for large systems, ab initio molecular dynamics, and high-throughput searches for functional materials. DFT's accuracy and computational efficiency are limited by the approximation to its exchange-correlation energy. Currently, the local density approximation (LDA) and generalized gradient approximations (GGAs) dominate materials computation mainly due to their efficiency. We show here that the recently developed non-empirical strongly constrained and appropriately normed (SCAN) meta-GGA improves significantly over LDA and the standard Perdew-Burke-Ernzerhof GGA for geometries and energies of diversely-bonded materials (including covalent, metallic, ionic, hydrogen, and van der Waals bonds) at comparable efficiency. Thus SCAN may be useful even for soft matter. Often SCAN matches or improves upon the accuracy of a computationally expensive hybrid functional, at almost-GGA cost. SCAN is therefore expected to have a broad impact on materials science.
Semiconductor nanowires (NWs) have been studied extensively for over two decades for their novel electronic, photonic, thermal, electrochemical and mechanical properties. This comprehensive review article summarizes major advances in the synthesis, characterization, and application of these materials in the past decade. Developments in the understanding of the fundamental principles of “bottom‐up” growth mechanisms are presented, with an emphasis on rational control of the morphology, stoichiometry, and crystal structure of the materials. This is followed by a discussion of the application of nanowires in i) electronic, ii) sensor, iii) photonic, iv) thermoelectric, v) photovoltaic, vi) photoelectrochemical, vii) battery, viii) mechanical, and ix) biological applications. Throughout the discussion, a detailed explanation of the unique properties associated with the one‐dimensional nanowire geometry will be presented, and the benefits of these properties for the various applications will be highlighted. The review concludes with a brief perspective on future research directions, and remaining barriers which must be overcome for the successful commercial application of these technologies.
Pair-distribution function and its coupling
