Generalized generalized gradient approximation: An improved density-functional theory for accurate orbital eigenvalues

The generalized gradient approximation (GGA) for the exchange functional in conjunction with accurate expressions for the correlation functional have led to numerous applications in which density-functional theory (DFT) provides structures, bond energies, and reaction activation energies in excellent agreement with the most accurate ab initio calculations and with the experiment. However, the orbital energies that arise from the Kohn-Sham auxiliary equations of DFT may differ by a factor of 2 from the ionization potentials, indicating that excitation energies and properties involving sums over excited states (nonlinear-optical properties, van der Waals attraction) may be in serious error.mWe propose herein a generalization of the GGA in which the changes in the functionals due to virtual changes in the orbitals are allowed to differ from the functional used to map the exact density onto the exact energy. Using the simplest version of this generalized GGA we show that orbital energies are within ∼5% of the correct values and the long-range behavior has the correct form

QM(DFT) and MD studies on formation mechanisms of C_(60) fullerenes

One of the most puzzling aspects of fullerenes is how such complicated symmetric molecules are formed from a gas of atomic carbons, namely, the atomistic or chemical mechanisms. Are the atoms added one by one or as molecules (C2, C3)? Is there a critical nucleus beyond which formation proceeds at gas kinetic rates? What determines the balance between forming buckyballs, buckytubes, graphite and soot? The answer to these questions is extremely important in manipulating the systems to achieve particular products. A difficulty in current experiments is that the products can only be detected on time scales of microseconds long after many of the important formation steps have been completed. Consequently, it is necessary to use simulations, quantum mechanics and molecular dynamics, to determine these initial states. Experiments serve to provide the boundary conditions that severely limit the possibilities. Using quantum mechanical methods (density functional theory (DFT)) we derived a force field (MSXX FF) to describe one-dimensional (rings) and two-dimensional (fullerene) carbon molecules. Combining DFT with the MSXX FF, we calculated the energetics for the ring fusion spiral zipper (RFSZ) mechanism for formation of C60 fullerenes. Our results shows that the RFSZ mechanism is consistent with the quantum mechanics (with a slight modification for some of the intermediates)

Band structures of II-VI semiconductors using Gaussian basis functions with separable ab initio pseudopotentials: Application to prediction of band offsets

We describe the implementation of a separable pseudopotential into the dual space approach for ab initio density-functional calculations using Gaussian basis functions. We apply this Gaussian dual space method (GDS/DFT) to the study of II-VI semiconductors (II=Zn, Cd, Hg; VI=S, Se, Te, Po). The results compare well with experimental data and demonstrate the general transferability of the separable pseudopotential. We also introduce a band-consistent tight-binding (BC-TB) model for calculating the bulk contributions to the valence-band offsets (VBO’s). This BC-TB approach yields good agreement with all-electron ab initio GDS/DFT results. Comparisons between BC-TB results of VBO obtained with and without p-d coupling demonstrate quantitatively the importance of d electrons and cation-d–anion-p coupling in II-VI systems. Agreement between ab initio results and experimental results is excellent

First principles studies of band offsets at heterojunctions and of surface reconstruction using Gaussian dual-space density functional theory

The use of localized Gaussian basis functions for large scale first principles density functional calculations with periodic boundary conditions (PBC) in 2 dimensions and 3 dimensions has been made possible by using a dual space approach. This new method is applied to the study of electronic properties of II–VI (II=Zn, Cd, Hg; VI=S, Se, Te, Po) and III–V (III=Al, Ga; V=As, N) semiconductors. Valence band offsets of heterojunctions are calculated including both bulk contributions and interfacial contributions. The results agree very well with available experimental data. The p(2 × 1) cation terminated surface reconstructions of CdTe and HgTe (100) are calculated using the local density approximation (LDA) with two-dimensional PBC and also using the ab initio Hartree–Fock (HF) method with a finite cluster. The LDA and HF results do not agree very well

Tree plantations displacing native forests: The nature and drivers of apparent forest recovery on former croplands in Southwestern China from 2000 to 2015

China is credited with undertaking some of the world's most ambitious policies to protect and restore forests, which could serve as a role model for other countries. However, the actual environmental consequences of these policies are poorly known. Here, we combine remote-sensing analysis with household interviews to assess the nature and drivers of land-cover change in southwestern China between 2000–2015, after China's major forest protection and reforestation policies came into effect. We found that while the region's gross tree cover grew by 32%, this increase was entirely due to the conversion of croplands to tree plantations, particularly monocultures. Native forests, in turn, suffered a net loss of 6.6%. Thus, instead of truly recovering forested landscapes and generating concomitant environmental benefits, the region's apparent forest recovery has effectively displaced native forests, including those that could have naturally regenerated on land freed up from agriculture. The pursuit of profit from agricultural or forestry production along with governmental encouragement and mobilization for certain land uses – including tree planting – were the dominant drivers of the observed land-cover change. An additional driver was the desire of many households to conform with the land-use decisions of their neighbors. We also found that households' lack of labor or financial resources, rather than any policy safeguards, was the primary constraint on further conversion of native forests. We conclude that to achieve genuine forest recovery along with the resulting environmental benefits, China's policies must more strongly protect existing native forests and facilitate native forest restoration. Natural regeneration, which thus far has been grossly neglected in China's forest policies, should be recognized as a legitimate means of forest restoration. In addition, social factors operating at the household level, notably the pursuit of profit and conformation to social norms, should be harnessed to promote better land-cover, biodiversity, and environmental outcomes. More generally, for China and other countries to succeed in recovering forests, policies must clearly distinguish between native forests and tree plantations

Improvement of hydrothermal stability of zeolitic imidazolate frameworks

The metal-organic framework ZIF-8, which undergoes hydrolysis under hydrothermal conditions, is endowed with high water-resistance after a shell-ligand-exchange-reaction. The stabilized ZIF-8 retains its structural characteristics with improved application performances in adsorption and membrane separation. © 2013 The Royal Society of Chemistry

First principles studies of band offsets at heterojunctions and of surface reconstruction using Gaussian dual-space density functional theory

The use of localized Gaussian basis functions for large scale first principles density functional calculations with periodic boundary conditions ͑PBC͒ in 2 dimensions and 3 dimensions has been made possible by using a dual space approach. This new method is applied to the study of electronic properties of II-VI ͑IIϭZn, Cd, Hg; VIϭS, Se, Te, Po͒ and III-V ͑IIIϭAl, Ga; VϭAs, N͒ semiconductors. Valence band offsets of heterojunctions are calculated including both bulk contributions and interfacial contributions. The results agree very well with available experimental data. The p͑2ϫ1͒ cation terminated surface reconstructions of CdTe and HgTe ͑100͒ are calculated using the local density approximation ͑LDA͒ with two-dimensional PBC and also using the ab initio Hartree-Fock ͑HF͒ method with a finite cluster. The LDA and HF results do not agree very well

Constraint of a ruthenium-carbon triple bond to a five-membered ring

含过渡金属碳三键(M≡C)的金属卡拜化合物是许多有机反应的催化剂或关键中间体。对其合成及性质的研究是金属有机化学的热点之一。由于卡拜碳的sp杂化方式，大部分金属卡拜化合物均为链状结构（卡拜碳键角理想值为180 °），环内金属卡拜化合物因存在很大的环张力而难于合成。夏海平教授课题组发展了由链状多炔（称之为碳龙）构筑碳龙配合物的高效方法（Nature Communications, 2017, 8, 1912），实现了锇杂戊搭炔/烯及其衍生物的一锅法合成。现在，他们把该方法进一步拓展到了第二过渡系金属钌，通过碳龙与市售的RuCl2(PPh3)3反应一锅合成了钌杂戊搭炔I。本研究是碳龙化学的进一步延伸和发展，首次把碳龙化学的金属中心由锇拓展到了其它金属，展示了碳龙化学广阔的发展空间。该研究工作在夏海平教授指导下完成，能源材料化学协同创新中心（iChEM）博士后卓庆德和张弘副教授为共同第一作者。iChEM博士后周小茜、博士生陈志昕、林剑锋、卓凯玥、硕士康慧君、林鑫磊参与了部分实验工作。博士生华煜晖负责理论计算。【Abstract】The incorporation of a metal-carbon triple bond into a ring system is challenging because of the linear nature of triple bonds. To date, the synthesis of these complexes has been limited to those containing third-row transition metal centers, namely, osmium and rhenium. We report the synthesis and full characterization of the first cyclic metal carbyne complex with a second-row transition metal center, ruthenapentalyne. It shows a bond angle of 130.2(3)° around the sp-hybridized carbyne carbon, which represents the recorded smallest angle of second-row transition metal carbyne complexes, as it deviates nearly 50° from the original angle (180°). Density functional theory calculations suggest that the inherent aromatic nature of these metallacycles with bent Ru≡C–C moieties enhances their stability. Reactivity studies showed striking observations, such as ambiphilic reactivity, a metal-carbon triple bond shift, and a [2 + 2] cycloaddition reaction with alkyne and cascade cyclization reactions with ambident nucleophiles.This research was supported by the National Key R&D Program of China (2017YFA0204902) and the National Natural Science Foundation of China (nos. 21490573,21332002, and 21561162001). 研究工作得到国家自然科学基金项目（21490573、21332002 和21561162001）和国家重点研发计划（2017YFA0204902）的资助