Shubin Liu, Professor (刘述斌教授)
Research Computing Center
University of North Carolina
Chapel Hill, NC 27599-3420, USA

Density functional theory (DFT) has been well accepted as the most successful development in theoretical and computational chemistry in last few decades. Nevertheless, for most people, it is only a computational approach. It lacks well behind in offering chemical understanding and conceptualization. A similar situation occurred many years ago in the development of the molecular orbital theory, whose computational methodology matured well ahead of its chemical conceptualization and understanding such as the frontier orbital theory and Woodward–Hoffmann rules.

Using density or its associated quantities to appreciate the molecular structure, bonding, and reactivity can be witnessed by Bader’s Atoms-In-Molecules theory. It is, however, Robert G. Parr of University of North Carolina, USA, who pioneered this field with the establishment of the theoretical framework called Conceptual DFT. Formulization of concepts such as electronegativity, hardness/softness, Fukui function, electrophilicity, and dual descriptor is a few well-known examples of chemical concepts from DFT. More recent developments have also been reported in the literature.

In this special issue, to promote efforts to quantify chemical understanding in terms of DFT, we invite experts from across the world to present their recent results on this topic. This issue is not simply just another occasion to bring together people with the same interest. Rather, it serves as a reminder to our readers—especially students—that newcomers are welcome to contribute and opportunities are abundant.

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 Chemical Bonding and Interpretation of Time-Dependent Electronic Processes with Maximum Probability Domains SAVIN Andreas 物理化学学报   2018,34(5 ):528 -536. DOI:10.3866/PKU.WHXB201710111 摘要  （567） HTML （3） PDF（pc） （7348KB）（310） Tools have been designed obtain information about chemical bonds from quantum mechanical calculations. They work well for solutions of the stationary Schrödinger equation, but it is not clear whether Lewis electron pairs they aim to reproduce survive in time-dependent processes, in spite of the underlying Pauli principle being obeyed in this regime. A simple model of two same-spin non-interacting fermions in a one-dimensional box with an opaque wall, is used to study this problem, because it allows presenting the detailed structure of the wave function. It is shown that ⅰ) oscillations persisting after the Hamiltonian stopped changing produce for certain time intervals states where Lewis electron pairs are spatially separated, and ⅱ) methods (like density analysis, or the electron localization function) that are widely used for describing bonding in the stationary case, have limitations in such situations. An exception is provided by the maximum probability domain (the spatial domain that maximizes the probability to find a given number of particles in it). It is conceptually simple, and satisfactorily describes the phenomenon. 参考文献丨 相关文章丨 多维度评价
 Chemical Concepts from Density Functional Theory LIU Shubin.,ZHANG Xiaojuan. 物理化学学报   2018,34(6 ):563 -566. DOI:10.3866/PKU.WHXB201802282 摘要  （668） HTML （2） PDF（pc） （229KB）（292） Chemical concepts such as structure, bonding, reactivity, etc. have been widely used in the literature and text books to appreciate molecular properties and chemical transformations. Even though modern theoretical and computational chemistry is well established from the perspective of accuracy and complexity, how to quantify these concepts is a still unresolved task. Conceptual density functional theory and its related recent developments provide unique opportunities to tackle this problem. In this Special Issue, 27 contributions from top investigators over the world are collected to highlight the state-of-art research on this topic, which not only showcases the status of where we are now but also unveils a number to possible future directions to be pursued. 参考文献丨 相关文章丨 多维度评价
 Analogies between Density Functional Theory Response Kernels and Derivatives of Thermodynamic State Functions GEERLINGS Paul,DE PROFT Frank,FIAS Stijn 物理化学学报   2018,34(6 ):699 -707. DOI:10.3866/PKU.WHXB201711221 摘要  （592） HTML （4） PDF（pc） （325KB）（266） In view of its use as reactivity theory, Conceptual Density Functional Theory (DFT), introduced by Parr et al., has mainly concentrated up to now on the E = E[N, v] functional. However, different ensemble representations can be used involving other variables also, such as ρ and μ. In this study, these different ensemble representations (E, ?, F, and R) are briefly reviewed. Particular attention is then given to the corresponding second-order (functional) derivatives, and their analogies with the second-order derivatives of thermodynamic state functions U, F, H, and G, which are related to each other via Legendre transformations, just as the DFT functionals (Nalewajski and Parr, 1982). Starting from an analysis of the convexity/concavity of the DFT functionals, for which explicit proofs are discussed for some cases, the positive/negative definiteness of the associated kernels is derived and a detailed comparison is made with the thermodynamic derivatives.The stability conditions in thermodynamics are similar in structure to the convexity/concavity conditions for the DFT functionals. Thus, the DFT functionals are scrutinized based on the convexity/concavity of their two variables, to yield the possibility of establishing a relationship between the three second-order reactivity descriptors derived from the considered functional. Considering two ensemble representations, F and ?, F is eliminated as it has two dependent (extensive) variables, N and ρ. For ?, on the other hand, which is concave for both of its intensive variables (μ and υ), an inequality is derived from its three second-order (functional) derivatives: the global softness, the local softness, and the softness kernel. Combined with the negative value of the diagonal element of the linear response function, this inequality is shown to be compatible with the Berkowitz-Parr relationship, which relates the functional derivatives of ρ with υ, at constant N and μ. This was recently at stake upon quantifying Kohn’s Nearsightedness of Electronic Matter. The analogy of the resulting inequality and the thermodynamic inequality for the G derivatives is highlighted. Potential research paths for this study are briefly addressed; the analogies between finite-temperature DFT response functions and their thermodynamic counterparts and the quest for analogous relationships, as derived in this paper, for DFT functionals that are analogues of entropy-dimensioned thermodynamic functions such as the Massieu function. 参考文献丨 相关文章丨 多维度评价
 Quantitative Electrophilicity Measures GONZÁLEZ Marco Martínez,CÁRDENAS Carlos,RODRÍGUEZ Juan I.,LIU Shubin,HEIDAR-ZADEH Farnaz,MIRANDA-QUINTANA Ramón Alain,AYERS Paul W. 物理化学学报   2018,34(6 ):662 -674. DOI:10.3866/PKU.WHXB201711021 摘要  （1585） HTML （7） PDF（pc） （1264KB）（329） Quantitative correlation of several theoretical electrophilicity measures over different families of organic compounds are examined relative to the experimental values of Mayr et al. Notably, the ability to predict these values accurately will help to elucidate the reactivity and selectivity trends observed in charge-transfer reactions. A crucial advantage of this theoretical approach is that it provides this information without the need of experiments, which are often demanding and time-consuming. Here, two different types of electrophilicity measures were analyzed. First, models derived from conceptual density functional theory (c-DFT), including Parr’s original proposal and further generalizations of this index, are investigated. For instance, the approaches of Gázquez et al. and Chamorro et al. are considered, whereby it is possible to distinguish between processes in which a molecule gains or loses electrons. Further, we also explored two novel electrophilicity definitions. On one hand, the potential of environmental perturbations to affect electron incorporation into a system is analyzed in terms of recent developments in c-DFT. These studies highlight the importance of considering the molecular surroundings when a consistent description of chemical reactivity is needed. On the other hand, we test a new definition of electrophilicity that is free from inconsistencies (so-called thermodynamic electrophilicity). This approach is based on Parr’s pioneering insights, though it corrects issues present in the standard working expression for the calculation of electrophilicity. Additionally, we use machine-learning tools (i.e., symbolic regression) to identify the models that best fit the experimental values. In this way, the best possible description of the electrophilicity values in terms of different electronic structure quantities is obtained. Overall, this straightforward approach enables one to obtain good correlations between the theoretical and experimental quantities by using the simple, yet powerful, interpretative advantage of c-DFT methods. In general, we observed that the correlations found at the HF/6-31G(d) level of theory are of semi-quantitative value. To obtain more accurate results, we showed that working with families of compounds with similar functional groups is indispensable. 参考文献丨 相关文章丨 多维度评价
 Levy Constrained Search in Fock Space: An Alternative Approach to Noninteger Electron Number AYERS Paul W.,LEVY Mel 物理化学学报   2018,34(6 ):625 -630. DOI:10.3866/PKU.WHXB201711071 摘要  （474） HTML （1） PDF（pc） （308KB）（205） By extending the Levy wavefunction constrained search to Fock Space, one can define a wavefunction constrained search for electron densities in systems having noninteger number of electrons. For pure-state v-representable densities, the results are equivalent to what one would obtain with the zero-temperature grand canonical ensemble. In other cases, the wavefunction constrained search in Fock space presents an upper bound to the grand canonical ensemble functional. One advantage of the Fock-space wavefunction constrained search functional over the zero-temperature grand-canonical ensemble constrained search functional is that certain specific excited states (i.e., those that are not ground-state v-representable) are the stationary points of the Fock-space functional. However, a potential disadvantage of the Fock-space constrained search functional is that it is not convex. 参考文献丨 相关文章丨 多维度评价
 Reactivity of Indoles through the Eyes of a Charge-Transfer Partitioning Analysis OROZCO-VALENCIA Ulises,GÁZQUEZ José L.,VELA Alberto 物理化学学报   2018,34(6 ):692 -698. DOI:10.3866/PKU.WHXB201801121 摘要  （689） HTML （1） PDF（pc） （611KB）（192） A global and local charge transfer partitioning model, based on the cornerstone theory developed by Robert G. Parr and Robert G. Pearson, which introduces two charge transfer channels (one for accepting electrons (electrophilic) and another for donating (nucleophilic)), is applied to the reaction of a set of indoles with 4, 6-dinitrobenzofuroxan. The global analysis indicates that the prevalent electron transfer mechanism in the reaction is a nucleophilic one on the indoles, i.e., the indoles under consideration transfer electrons to 4, 6-dinitrobenzofuroxan. Evaluating the reactivity descriptors with exchange-correlation functionals including exact exchange (global hybrids) yields slightly better correlations than those obtained with generalized gradient-approximated functionals; however, the trends are preserved. Comparing the trend obtained with the number of electrons donated by the indoles, and predicted by the partitioning model, with that observed experimentally based on the measured rate constants, we propose that the number of electrons transferred through this channel can be used as a nucleophilicity scale to order the reactivity of indoles towards 4, 6-dinitrobenzofuroxan. This approach to obtain reactivity scales has the advantage of depending on the intrinsic properties of the two reacting species; therefore, it opens the possibility that the same group of molecules may show different reactivity trends depending on the species with which they are reacting. The local model allows systematic incorporation of the reactive atoms based on the their decreasing condensed Fukui functions, and the correlations obtained by increasing the number of reactive atoms participating in the local analysis of the transferred nucleophilic charge improve, reaching an optimal correlation, which in the present case indicates keeping three atoms from the indoles and two from 4, 6-dinitrobenzofuroxan. The atoms selected by this procedure provide valuable information about the local reactivity of the indoles. We further show that this information about the most reactive atoms on each reactant, combined with the spatial distribution of the nucleophilic and electrophilic Fukui functions of both reactants, allows one to propose non-trivial candidates of starting geometries for the search of the transition state structures present in these reactions. 参考文献丨 相关文章丨 多维度评价
 通过价层电子密度分析展现分子电子结构 卢天,陈沁雪 物理化学学报   2018,34(5 ):503 -513. DOI:10.3866/PKU.WHXB201709252 摘要  （2111） HTML （41） PDF（pc） （3997KB）（1002） 迄今已有众多实空间函数被提出用来揭示化学上感兴趣的分子电子结构特征，例如化学键、孤对电子和多中心电子共轭。在这些分析方法中，电子定域化函数(ELF)、电子密度的拉普拉斯(∇2ρ)和变形密度(ρdef)被广泛用于实际研究。众所周知，分析分子的总电子密度无法像以上提及的方法那样展现出与分子电子结构有关的丰富的信息。但是，在本文中，通过数个实例以及通过与ELF、∇2ρ和ρdef的对比，我们指出若只关注价层电子密度分布，分子电子结构特征也是可能被探究的。我们发现对大多数情况，对非常简单的价层电子密度的分析也可以给出与ELF、∇2ρ和ρdef分析类似的信息，并且这种分析具有计算复杂度更低的额外优点。我们希望本文的工作可以使得化学家们关注长期被忽视的价层电子密度所具有的重要价值。也值得注意的是，价层电子密度分析并非完全没有缺点，当这种方法无法提供丰富信息的时候，研究者仍需借助于其它类型的分析手段。 参考文献丨 相关文章丨 多维度评价
 Effect of Pressure on Cesium Iodide Band Gap CEDILLO Andrés,CORTONA Pietro 物理化学学报   2018,34(2 ):208 -212. DOI:10.3866/PKU.WHXB201707031 摘要  （867） HTML （1） PDF（pc） （713KB）（521） The evolution of cesium iodide band gap as a function of pressure is studied in the range from 0 to 60 GPa. Within this range, two structural phase transitions occurred, and the band gap was affected by the compression pressure and structural rearrangement. The band gap estimation under pressure, as obtained by the density functional theory methods, successfully reproduced the experimental trend of the optical gap and electrical resistivity, namely, a general decreasing tendency, an early maximum, and a discontinuous peak around 40 GPa. 参考文献丨 相关文章丨 多维度评价
 Perspective: Chemical Information Encoded in Electron Density CONTRERAS-GARCíA Julia,YANG Weitao 物理化学学报   2018,34(6 ):567 -580. DOI:10.3866/PKU.WHXB201801261 摘要  （1019） HTML （15） PDF（pc） （3954KB）（326） In this perspective, we review the chemical information encoded in electron density and other ingredients used in semilocal functionals. This information is usually looked at from the functional point of view: the exchange density or the enhancement factor are discussed in terms of the reduced density gradient. However, what parts of a molecule do these 3D functions represent? We look at these quantities in real space, aiming to understand the electronic structure information they encode and provide an insight from the quantum chemical topology (QCT). Generalized gradient approximations (GGAs) provide information about the presence of chemical interactions, whereas meta-GGAs can differentiate between the different bonding types. By merging these two techniques, we show new insight into the failures of semilocal functionals owing to three main errors: fractional charges, fractional spins, and non-covalent interactions. We build on simple models. We also analyze the delocalization error in hydrogen chains, showing the ability of QCT to reveal the delocalization error introduced by semilocal functionals. Then, we show how the analysis of localization can help understand the fractional spin error in alkali atoms, and how it can be used to correct it. Finally, we show that the poor description of GGAs of isodesmic reactions in alkanes is due to 1, 3-interactions. 参考文献丨 相关文章丨 多维度评价
 Which Information Theoretic Quantity Should We Choose for Steric Analysis of Water Nanoclusters (H2O)n (n = 6, 32, 64)? ALIPOUR Mojtaba 物理化学学报   2018,34(4 ):407 -413. DOI:10.3866/PKU.WHXB201708175 摘要  （779） HTML （7） PDF（pc） （2621KB）（332） As evidenced from recent literature, interest in employing information theory measures for understanding different properties of atomic and molecular systems is increasing tremendously. Following our earlier efforts in this field, we here evaluate the feasibility of using information theory functionals such as Fisher information, Shannon entropy, Onicescu information energy, and Ghosh-Berkowitz-Parr entropy as measures of steric effects for the steric analysis of water nanoclusters. Taking the structural isomers of water hexamers as working models and using information theoretic quantities, we show that the relative energies of water nanoclusters and the computed steric energies are related. We also show the strong effects of steric repulsion on conformational stabilities. At the same time, we have also assessed the usefulness of simultaneously considering the different information theoretic quantities, and achieved more accurate descriptions of the stability of water nanoclusters. In order to consider the effects of cluster size on the obtained results and the extent of applicability of information theoretic quantities, we have also benchmarked larger water nanoclusters with 32 and 64 units. Scrutinizing the obtained data from information theory functionals, we found that Fisher information shows the best overall performance. Our findings underline that the information theoretic quantities, especially Fisher information, can be used as quantitative measures of relative energies and consequently the order of stability of nanoclusters, which affirmed the utility of information theory for investigating various physical and chemical problems. 参考文献丨 相关文章丨 多维度评价
 Quantifying Electronic Effects in QM and QM/MM Biomolecular Modeling with the Fukui Function QI Helena W.,KARELINA Maria,KULIK Heather J 物理化学学报   2018,34(1 ):81 -91. DOI:10.3866/PKU.WHXB201706303 摘要  （1029） HTML （10） PDF（pc） （2169KB）（673） Multi-scale quantum-mechanical/molecular-mechanical (QM/MM) and large-scale QM simulation provide valuable insight into enzyme mechanism and structure-property relationships. Analysis of the electron density afforded through these methods can enhance our understanding of how the enzyme environment modulates reactivity at the enzyme active site. From this perspective, tools from conceptual density functional theory to interrogate electron densities can provide added insight into enzyme function. We recently introduced the highly parallelizable Fukui shift analysis (FSA) method, which identifies how frontier states of an active site are altered by the presence of an additional QM residue to identify when QM treatment of a residue is essential as a result of quantum-mechanically affecting the behavior of the active site. We now demonstrate and analyze distance and residue dependence of Fukui function shifts in pairs of residues representing different non-covalent interactions. We also show how the interpretation of the Fukui function as a measure of relative nucleophilicity provides insight into enzymes that carry out SN2 methyl transfer. The FSA method represents a promising approach for the systematic, unbiased determination of quantum mechanical effects in enzymes and for other complex systems that necessitate multi-scale modeling. 参考文献丨 相关文章丨 多维度评价
 Multiply Charged Anions, Maximum Charge Acceptance, and Higher Electron Affinities of Molecules, Superatoms, and Clusters VON SZENTPÁLY László 物理化学学报   2018,34(6 ):675 -682. DOI:10.3866/PKU.WHXB201801021 摘要  （598） HTML （5） PDF（pc） （595KB）（178） The addition of electrons to form gas-phase multiply charged anions (MCAs) normally requires sophisticated experiments or calculations.In this work, the factors stabilizing the MCAs, the maximum electron uptake of gas-phase molecules, X, and the electronic stability of MCAs XQ-, are discussed. The drawbacks encountered when applying computational and/or conceptual density functional theory (DFT) to MCAs are highlighted. We develop and test a different model based on the valence-state concept. As in DFT, the electronic energy, E(N, vex), is a continuous function of the average electron number, N, and the external potential, vex, of the nuclei. The valence-state-parabola is a second-order polynomial that allows extending E(N, vex) to dianions and higher MCAs. The model expresses the maximum electron acceptance, Qmax, and the higher electron affinities, AQ, as simple functions of the first electron affinity, A1, and the ionization energy, I, of the “ancestor” system. Thus, the maximum electron acceptance is Qmax, calc = 1 + 12A1/7(I -A1). The ground-state parabola model of the conceptual DFT yields approximately half of this value, and it is termed Qmax, GS = ${}^{1}\!\!\diagup\!\!{}_{2}\;$ + A1/(I -A1). A large variety of molecules are evaluated including fullerenes, metal clusters, super-pnictogens, super-halogens (OF3), super-alkali species (OLi3), and neutral or charged transition-metal complexes, ABmLn0/+/-. The calculated second electron affinity A2, calc = A1-(7/12)(I -A1) is linearly correlated to the literature references A2, lit with a correlation coefficient R = 0.998. A2 or A3 values are predicted for further 24 species. The appearance sizes, nap3-, of triply charged anionic clusters and fullerenes are calculated in agreement with the literature. 参考文献丨 相关文章丨 多维度评价
 Kohn-Sham Density Matrix and the Kernel Energy Method POLKOSNIK Walter,MASSA Lou 物理化学学报   2018,34(6 ):656 -661. DOI:10.3866/PKU.WHXB201801101 摘要  （416） HTML （1） PDF（pc） （510KB）（128） The kernel energy method (KEM) has been shown to provide fast and accurate molecular energy calculations for molecules at their equilibrium geometries. KEM breaks a molecule into smaller subsets, called kernels, for the purposes of calculation. The results from the kernels are summed according to an expression characteristic of KEM to obtain the full molecule energy. A generalization of the kernel expansion to density matrices provides the full molecule density matrix and orbitals. In this study, the kernel expansion for the density matrix is examined in the context of density functional theory (DFT) Kohn-Sham (KS) calculations. A kernel expansion for the one-body density matrix analogous to the kernel expansion for energy is defined, and is then converted into a normalized projector by using the Clinton algorithm. Such normalized projectors are factorizable into linear combination of atomic orbitals (LCAO) matrices that deliver full-molecule Kohn-Sham molecular orbitals in the atomic orbital basis. Both straightforward KEM energies and energies from a normalized, idempotent density matrix obtained from a density matrix kernel expansion to which the Clinton algorithm has been applied are compared to reference energies obtained from calculations on the full system without any kernel expansion. Calculations were performed both for a simple proof-of-concept system consisting of three atoms in a linear configuration and for a water cluster consisting of twelve water molecules. In the case of the proof-of-concept system, calculations were performed using the STO-3G and 6-31G(d, p) bases over a range of atomic separations, some very far from equilibrium. The water cluster was calculated in the 6-31G(d, p) basis at an equilibrium geometry. The normalized projector density energies are more accurate than the straightforward KEM energy results in nearly all cases. In the case of the water cluster, the energy of the normalized projector is approximately four times more accurate than the straightforward KEM energy result. The KS density matrices of this study are applicable to quantum crystallography. 参考文献丨 相关文章丨 多维度评价
 Generalized Hirshfeld Partitioning with Oriented and Promoted Proatoms HEIDAR-ZADEH Farnaz,AYERS Paul W. 物理化学学报   2018,34(5 ):514 -518. DOI:10.3866/PKU.WHXB201710101 摘要  （476） HTML （3） PDF（pc） （294KB）（223） In this study, we show how to generalize Hirshfeld partitioning methods to possibly include non-spherical proatom densities. While this generalization is numerically challenging (requiring global optimization of a large number of parameters), it is conceptually appealing because it allows the proatoms to be pre-polarized, or even promoted, to a state that more closely resembles the atom in a molecule. This method is based on first characterizing the convex set of proatom densities associated with the degenerate ground states of isolated atoms and atomic ions. The preferred orientation of the proatoms' densities are then obtained by minimizing the information–theoretic distance between the promolecular and molecular densities. If contributions from excited states (and not just degenerate ground states) are included in the convex set, this method can describe promoted atoms. While the procedure is intractable in general, if one includes only atomic states that have differing electron-numbers and/or spins, the variational principle becomes a simple convex optimization with a single unique solution. 参考文献丨 相关文章丨 多维度评价
 Understanding Chemical Reactivity in Extended Systems: Exploring Models of Chemical Softness in Carbon Nanotubes CÁRDENAS Carlos,MUÑOZ Macarena,CONTRERAS Julia,AYERS Paul W.,GÓMEZ Tatiana,FUENTEALBA Patricio 物理化学学报   2018,34(6 ):631 -638. DOI:10.3866/PKU.WHXB201710201 摘要  （596） HTML （1） PDF（pc） （1663KB）（385） Chemical reactivity towards electron transfer is captured by the Fukui function. However, this is not well defined when the system or its ions have degenerate or pseudo-degenerate ground states. In such a case, the first-order chemical response is not independent of the perturbation and the correct response has to be computed using the mathematical formalism of perturbation theory for degenerate states. Spatial pseudo-degeneracy is ubiquitous in nanostructures with high symmetry and totally extended systems. Given the size of these systems, using degenerate-state perturbation theory is impractical because it requires the calculation of many excited states. Here we present an alternative to compute the chemical response of extended systems using models of local softness in terms of the local density of states. The local softness is approximately equal to the density of states at the Fermi level. However, such approximation leaves out the contribution of inner states. In order to include and weight the contribution of the states around the Fermi level, a model inspired by the long-range behavior of the local softness is presented. Single wall capped carbon nanotubes (SWCCNT) illustrate the limitation of the frontier orbital theory in extended systems. Thus, we have used a C360 SWCCNT to test the proposed model and how it compares with available models based on the local density of states. Interestingly, a simple Hückel approximation captures the main features of chemical response of these systems. Our results suggest that density-of-states models of the softness along simple tight binding Hamiltonians could be used to explore the chemical reactivity of more complex system, such a surfaces and nanoparticles. 参考文献丨 相关文章丨 多维度评价
 The Influence of the Exchange-Correlation Functional on the Non-Interacting Kinetic Energy and Its Implications for Orbital-Free Density Functional Approximations FINZEL Kati.,BULTINCK Patrick. 物理化学学报   2018,34(6 ):650 -655. DOI:10.3866/PKU.WHXB201710251 摘要  （532） HTML （1） PDF（pc） （344KB）（240） In this work it is shown that the kinetic energy and the exchange-correlation energy are mutual dependent on each other. This aspect is first derived in an orbital-free context. It is shown that the total Fermi potential depends on the density only, the individual parts, the Pauli kinetic energy and the exchange-correlation energy, however, are orbital dependent and as such mutually influence each other. The numerical investigation is performed for the orbital-based non-interacting Kohn-Sham system in order to avoid additional effects due to further approximations of the kinetic energy. The numerical influence of the exchange-correlation functional on the non-interacting kinetic energy is shown to be of the order of a few Hartrees. For chemical purposes, however, the energetic performance as a function of the nuclear coordinates is much more important than total energies. Therefore, the effect on the bond dissociation curve was studied exemplarily for the carbon monoxide. The data reveals that, the mutual influence between the exchange-correlation functional and the kinetic energy has a significant influence on bond dissociation energies and bond distances. Therefore, the effect of the exchange-correlation treatment must be considered in the design of orbital-free density functional approximations for the kinetic energy. 参考文献丨 相关文章丨 多维度评价
 Thermodynamic Dual Descriptor FRANCO-PÉREZ Marco,GÁZQUEZ José L.,AYERS Paul W.,VELA Alberto 物理化学学报   2018,34(6 ):683 -391. DOI:10.3866/PKU.WHXB201801031 摘要  （447） HTML （4） PDF（pc） （379KB）（154） A new definition of the dual descriptor, namely, the thermodynamic dual descriptor, is developed within the grand canonical potential formalism. This new definition is formulated to describe the same physical phenomenon as the original definition proposed by Morell, Grand, and Toro-Labbé (J. Phys. Chem. A 2005, 109, 205), which is characterized by a second-order response of the electron density towards an electron flux. To formulate the new definition, we performed two successive partial derivatives of the average electron density, one with respect to the average number of electrons, and the other with respect to the chemical potential of the electron reservoir. When the derivative is expressed in terms of the three-state ensemble model, in the regime of low temperatures up to temperatures of chemical interest, one finds that the thermodynamic dual descriptor can be expressed as ∆fT(r) = (β/2)C[f+(r)-f-(r)], where β = 1/kBT, C is a global quantity that depends on the temperature and global electronic properties of the molecule (the first ionization potential and the electron affinity), C = 1 for systems with zero fractional charge, and C = Cω > 0 (albeit very close to zero) for systems with nonzero fractional charge, , and f+(r) and f-(r) are the nucleophilic and electrophilic Fukui functions, respectively. The quantity within the square brackets is the original definition of the dual descriptor. As the local terms (the ones containing regioselectivity information) are equal to those of the dual descriptor, ∆fT(r) has the same regioselectivity information, multiplied by the global quantity (β/2)C. This implies that the regioselectivity information contained in the original dual descriptor is preserved at all temperatures different from zero, and for any value of C > 0. One of the most important features of this new definition is that it avoids the undesired Dirac delta behavior observed when the second order partial derivative of the average density is taken with respect to the average number of electrons, using the exact density dependence of the average number of electrons. 参考文献丨 相关文章丨 多维度评价
 从能量和信息理论视角理解单取代烷烃的异构化 钟爱国,李嵘嵘,洪琴,张杰,陈丹 物理化学学报   2018,34(3 ):303 -313. DOI:10.3866/PKU.WHXB201708302 摘要  （588） HTML （1） PDF（pc） （792KB）（383） 对直链烷烃和支链烷烃的相对稳定性统一的解释仍然没有定论，并且一直在进行着。以单取代的烷烃体系CnH2n+1―R (n = 3, 4, 5, 6；R = OH, OCH3, NH2, NO2, F, Cl, CN, CHO)为例，本文对支链效应的有效性和本质进行了研究。与传统的基于轨道的描述不同的是，本文采用了密度泛函理论的总能量和基于新能量分配方案的能量分量[见Liu, S. B. J. Chem. Phys. 2007, 126, 244103]。新型能量分解方法计算结果表明，静电效应和立体效应等对支链效应的存在都起着重要作用，但是它们均不能单独用来解释支链效应的本质。用双变量(静电势和空间位阻)组合，发现单取代烷烃衍生物的异构化反应主要影响因子是静电势作用，空间位阻效应的影响是次要的。此外还发现了香农熵差与Fisher信息差之间的线性关系，未能发现总能量差或者分能量差值和Fisher信息或者Shannon熵之间的关系。这与前人发现是一致的。 参考文献丨 相关文章丨 多维度评价
 运用密度泛函活性理论的信息论方法研究苯并富烯衍生物的芳香性 余东海,荣春英,卢天,DEPROFT Frank.,刘述斌 物理化学学报   2018,34(6 ):639 -649. DOI:10.3866/PKU.WHXB201710231 摘要  （1432） HTML （18） PDF（pc） （1604KB）（475） 文献中已有越来越多的芳香性体系被发现，同时也有越来越多的芳香性指标被提出来，但是如何解释芳香化合物稳定性的起源以及理解芳香性的本质仍然是当今理论化学中一个悬而未决的难题。运用我们新近提出的密度泛函活性理论信息论方法，不久前我们曾对一系列富烯衍生物进行了系统研究并得到了一个全新的认识。本文进一步探讨苯并富烯衍生物的芳香性行为，目的在于考察一个或多个苯环与富烯连接之后其芳香性发生变化的情况。运用香农熵，费舍尔信息，Ghosh-Berkowitz-Parr熵，Onicescu信息能，信息增益，以及相对Rényi熵六个信息量，和四种芳香指标，ASE，HOMA，FLU和NICS，我们系统地研究了信息量和芳香性指标在单、双、三苯并富烯衍生物中的相关性。我们发现，不管是否有苯环与富烯相连，芳香指标和信息量的交叉相关性都是一样的。这表明，虽然苯环本身具有芳香性，但苯环与富烯相连并不能改变富烯的芳香性与反芳香性本质。苯并富烯衍生物与富烯衍生物的芳香性和反芳香性一致。苯并富烯衍生物的芳香性和反芳香性完全取决于富烯本身的芳香性和反芳香性。这些结果为认识和理解复杂体系芳香性和反芳香性起源和本质将提供有益的启示。 参考文献丨 相关文章丨 多维度评价
 基于概念密度泛函理论磷酸酯类反应性物质毒性预测 丁晓琴,丁俊杰,李大禹,潘里,裴承新 物理化学学报   2018,34(3 ):314 -322. DOI:10.3866/PKU.WHXB201709042 摘要  （743） HTML （3） PDF（pc） （477KB）（438） 磷酸酯类反应性物质是乙酰胆碱酯酶不可逆抑制剂。本文应用概念密度泛函理论(CDFT)，采用四组条件(B3LYP/6-311++G(2d, 3p)/gas，B3LYP/6-311++G(2d, 3p)/CPCM/water，MP2/6-311++G(2d, 3p)/gas，MP2/6-311++ G(2d, 3p)/CPCM/water)，对20多个磷酸酯反应性物质进行反应性描述指数计算，包括分子的化学势μ，绝对硬度η、亲电性指数ω、分子的前线轨道能量等分子整体描述参数，以及原子福井函数、自然键轨道(NBO)电荷、Wiberg键级、NBO键级等分子局域描述参数。通过对反应性描述指数以及定量构性关系(QSPR)方程预测结果的比较分析，得出结论：大多数化合物亲电进攻的反应中心发生在磷原子上；磷酸酯类化合物侧链乙胺基叔氮的质子化，将显著增强反应中心磷原子的亲电进攻能力；B3LYP/6-311++G(2d, 3p)/gas为最合理的计算条件；应用反应性描述指数建立的QSPR模型明显优于常规的2D-QSPR模型，能够用于乙酰胆碱酯酶不可逆抑制剂的精确毒性预测。 参考文献丨 相关文章丨 多维度评价
 Adsorption of Hydrazoic Acid on Pristine Graphyne Sheet: A Computational Study DEB Jyotirmoy,PAUL Debolina,PEGU David,SARKAR Utpal 物理化学学报   2018,34(5 ):537 -542. DOI:10.3866/PKU.WHXB201710161 摘要  （593） HTML （3） PDF（pc） （951KB）（321） Herein we have investigated the interaction between hydrazoic acid (HN3) and a pristine graphyne system based on density functional theory (DFT) method using generalized gradient approximation. The van der Waals dispersion correction is also considered for predicting the possibility of using the graphyne system for detection of hydrazoic acid. Pristine graphyne has a band gap of 0.453 eV, which decreases to 0.424 eV when HN3 is adsorbed on graphyne. The electrical conductivity of HN3-adsorbed graphyne is greater than that of its pristine counterpart. Charge transfer analysis reveals that the HN3-adsorbed graphyne system behaves as an n-type semiconductor; however, its pristine analogue acts as an intrinsic semiconductor. Pristine graphyne has zero dipole moment; however, its interaction with HN3 increases its dipole moment. The electronic properties of graphyne is significantly influenced by the presence of HN3, leading to the possibility of designing graphyne-based sensors for HN3 detection. 参考文献丨 相关文章丨 多维度评价
 Bonding and Reactivity in RB-AsR Systems (R=H, F, OH, CH3, CMe3, CF3, SiF3, BO):Substituent Effects GHARA Manas,CHATTARAJ Pratim K. 物理化学学报   2018,34(2 ):201 -207. DOI:10.3866/PKU.WHXB201707131 摘要  （714） HTML （1） PDF（pc） （1220KB）（469） Density functional theory-based calculations have been carried out to study the bonding and reactivity in RB-AsR (R=H, F, OH, CH3, CMe3, CF3, SiF3, BO) systems. Our calculations demonstrated that all the studied systems adopted bent geometry (∠R-B-As ≈ 180° and ∠B-As-R ≈ 90° or less). The reason for this bending was explained with the help of a valence-orbital model. The potential energy surfaces for three possible isomers of RB-AsR systems were also generated, indicating that the RB-AsR isomer was more stable than R2B-AsR when R=SiF3, CMe3, and H. The B-As bond character was analyzed using natural bond orbital (NBO) and Wiberg bond index (WBI) calculations. The WBI values for B-As bonds in F3SiB-AsSiF3 and HB-AsH were 2.254 and 2.209, respectively, indicating that this bond has some triple-bond character in these systems. While the B centers prefer nucleophilic attack, the As centers prefer electrophilic attack. 参考文献丨 相关文章丨 多维度评价
 Fukui函数和局域软度应用于亲电加成反应的区位选择性的研究 朱尊伟,杨巧凤,徐珍珍,赵东霞,樊红军,杨忠志 物理化学学报   2018,34(5 ):519 -527. DOI:10.3866/PKU.WHXB201710126 摘要  （639） HTML （3） PDF（pc） （642KB）（300） Fukui函数、局域软度、广义Fukui函数以及广义软度通常被称为反应描述符。使用它们研究和探讨了HCl与不对称烯烃以及溴苯硒与不对称苯乙烯的亲电加成反应的区位选择性。在MP2/6-311++G(d, p)理论水平下，采用有限差分方法计算这些反应描述符，同时也使用ABEEMσπ方法进行了计算。ABEEMσπ模型下的局域软度和广义局域软度，分别结合局域硬-软酸碱(HSAB)原理，得出亲电试剂氯化氢与溴苯硒，更容易进攻不对称乙烯和苯乙烯中的马氏碳原子，符合马氏规则。而有限差分方法不能完全地解释该系列反应的区位选择性。此外，主要产物所对应的马氏碳原子的广义局域软度值，就能够预测出此类反应的活性序列，所得结果与速率常数有很好的关联。 参考文献丨 相关文章丨 多维度评价
 自然轨道福井函数和成键活性描述符应用于解释苯硫醌和1, 3-二烯的[2+4]和[4+2]环加成反应中的成键机理 闫超咸,杨帆,吴睿智,周大刚,杨兴,周盼盼 物理化学学报   2018,34(5 ):497 -502. DOI:10.3866/PKU.WHXB201709222 摘要  （850） HTML （7） PDF（pc） （807KB）（408） 苯硫醌与脂肪族烯烃可以发生[2+4]和[4+2]环加成反应。为了解释这些环加成反应中的成键过程，本文使用了自然轨道福井函数(NOFF)与成键活性描述符。自然轨道福井函数揭示了苯硫醌和脂肪族烯烃的键或轨道的亲电性，表明电子供体的成键轨道和电子受体的反键/成键轨道之间发生了电子转移，然后成环，在这一过程中有两个共价键形成，得到了环状产物。成键活性描述符表明共价键比较容易在一个分子中具有较大fk1+值的k1原子与另一个分子中具有较大fk2-值的k2原子之间形成。自然轨道福井函数与成键活性描述符都可以有效解释苯硫醌与1, 3-二烯之间的[2+4]与[4+2]环加成反应的机理。 参考文献丨 相关文章丨 多维度评价
 Phase Space View of Ensembles of Excited States NAGY Ágnes 物理化学学报   2018,34(5 ):492 -496. DOI:10.3866/PKU.WHXB201709221 摘要  （572） HTML （12） PDF（pc） （245KB）（278） The density functional theory and its extension to ensembles of excited states can be formalized as thermodynamics. However, these theories are not unique because one of their key quantities, the kinetic energy density, can be defined in several ways. Usually, the everywhere positive gradient form is applied; however, other forms are also acceptable, provided they integrate to the true kinetic energy. Recently, a kinetic energy density of the ground-state theory maximizing the information entropy has been proposed. Here, ensemble kinetic energy density, leading to extremum information entropy, is derived via constrained search. The corresponding ensemble temperature is found to be constant. 参考文献丨 相关文章丨 多维度评价
 Strength of Intramolecular Hydrogen Bonds JIANG Xiaoyu,WU Wei,MO Yirong 物理化学学报   2018,34(3 ):278 -285. DOI:10.3866/PKU.WHXB201708174 摘要  （817） HTML （17） PDF（pc） （637KB）（472） The concept of resonance-assisted hydrogen bonds (RAHBs) highlights the synergistic interplay between the π-resonance and hydrogen bonding interactions. This concept has been well-accepted in academia and is widely used in practice. However, it has been argued that the seemingly enhanced intramolecular hydrogen bonding (IMHB) in unsaturated compounds may simply be a result of the constraints imposed by the σ-skeleton framework. Thus, it is crucial to estimate the strength of IMHBs. In this work, we used two approaches to probe the resonance effect and estimate the strength of the IMHBs in the two exemplary cases of the enol forms of acetylacetone and o-hydroxyacetophenone. One approach is the block-localized wavefunction (BLW) method, which is a variant of the ab initio valence bond (VB) theory. Using this approach, it is possible to derive the geometries and energetics with resonance shut down. The other approach is Edmiston’s truncated localized molecular orbital (TLMO) technique, which monitors the energy changes by removing the delocalization tails from localized molecular orbitals. The integrated BLW and TLMO studies confirmed that the hydrogen bonding in these two molecules is indeed enhanced by π-resonance, and that this enhancement is not a result of σ constraints. 参考文献丨 相关文章丨 多维度评价
 Fukui Functions for the Temporary Anion Resonance States of Be-, Mg-, and Ca- MORRISON Robert C 物理化学学报   2018,34(3 ):263 -269. DOI:10.3866/PKU.WHXB201708173 摘要  （606） HTML （1） PDF（pc） （514KB）（273） In this work, the Fukui functions of the two 2P resonance states of Be-, a 2P resonance state of Mg-, and a 2D resonance state of Ca- have been determined. The trajectories of these resonance states, in conjunction with the complex rotation of the Hamiltonian, were used to determine their wave functions. The electron densities, Fukui functions, and values of the hyper-radius < r2 > were computed from these wave functions. The Fukui functions have negative regions in the valence shell in addition to the inner shell regions, indicating screening effects of the outer temporary electron. Selected configuration interactions with up to quadruple excitations were used along the trajectories and for computing the final wave function. Based on this data, the densities, Fukui functions, and < r2 > were calculated. 参考文献丨 相关文章丨 多维度评价
 Chemical Reactivity Description in Density-Functional and Information Theories NALEWAJSKI Roman F 物理化学学报   2017,33(12 ):2491 -2509. DOI:10.3866/PKU.WHXB201706132 摘要  （652） HTML （7） PDF（pc） （1033KB）（739） In Quantum Information Theory (QIT) the classical measures of information content in probability distributions are replaced by the corresponding resultant entropic descriptors containing the nonclassical terms generated by the state phase or its gradient (electronic current). The classical Shannon (S[p]) and Fisher (I[p]) information terms probe the entropic content of incoherent local events of the particle localization, embodied in the probability distribution p, while their nonclassical phase-companions, S[φ] and I[φ], provide relevant coherence information supplements. Thermodynamic-like couplings between the entropic and energetic descriptors of molecular states are shown to be precluded by the principles of quantum mechanics. The maximum of resultant entropy determines the phase-equilibrium state, defined by “thermodynamic” phase related to electronic density, which can be used to describe reactants in hypothetical stages of a bimolecular chemical reaction. Information channels of molecular systems and their entropic bond indices are summarized, the complete-bridge propagations are examined, and sequential cascades involving the complete sets of the atomic-orbital intermediates are interpreted as Markov chains. The QIT description is applied to reactive systems R=A-B, composed of the Acidic (A) and Basic (B) reactants. The electronegativity equalization processes are investigated and implications of the concerted patterns of electronic flows in equilibrium states of the complementarily arranged substrates are investigated. Quantum communications between reactants are explored and the QIT descriptors of the A-B bond multiplicity/composition are extracted. 参考文献丨 相关文章丨 多维度评价