In the recent work of S. Sharma \emph{et al.}, (arxiv.org: arxiv:0912.1118), a single-electron spectrum associated with the natural orbitals was defined as the derivative of the total energy with respect to the occupation numbers at half filling for the orbital of interest. This idea reproduces the bands of various periodic systems using the appropriate functional quite accurately. In the present work we apply this approximation to the calculation of the ionization potentials and electron affinities of molecular systems using various functionals within the reduced density-matrix functional theory. We demonstrate that this approximation is very successful in general and in particular for certain functionals it performs better than the direct determination of the ionization potentials and electron affinities through the calculation of positive and negative ions respectively. The reason for this is identified to be the inaccuracy that arises from different handling of the open- and closed-shell systems.
Assessment of W1 and W2 theories for the computation of electron affinities, ionization potentials, heats of formation, and proton affinities
本文介绍了两种新的{ \em ab initio}计算热化学方法，W1和W2理论[J.M.L. Martin和G. de Oliveira，J.Chem.Phys.111，1843（1999）]，评估了由G2-1和G2-2集合中的电离势和电子亲合势以及G2 -1和G2 -2集合的子集中的生成热组成的热化学数据的放大样本。我们发现W1理论对于电离势和电子亲合势的精确度比常用的（并且更便宜的）计算热化学方案（如G2，G3和CBS-QB 3）高出几倍：W2理论对于电子亲合势略有改善，但对于电离势没有显著改善。使用两点的$A+B/L^5$，而不是一个三点的$A+B/C^L$外推的SCF组件大大提高了数值稳定性的W1方法的系统与缓慢的基组收敛。包含一阶自旋轨道耦合对于精确的电离势和涉及简并电子态的电子亲合势是必不可少的：内壳层相关对于电离势比电子亲合势更重要，而标量相对论效应则需要最高的精度。G2-1生成热与实验的平均偏差在平均实验不确定度范围内。W1理论似乎是一个有价值的工具，获得基准质量的质子亲和力。
Quantum self-consistent equation-of-motion method for computing molecular excitation energies, ionization potentials, and electron affinities on a quantum computer
Ionization Energies, Electron Affinities, Bandgaps, Exciton Binding Energies, and Polarization Energies of Orientation-Controlled Picene, [6]-Phenacene, and [7]-Phenacene Thin Films
Chiba University（千叶大学）；Kyushu Institute of Technology（九州工业大学）；Institute for Molecular Science, National Institutes of Natural Sciences（国立自然科学研究所分子科学研究所）；The Graduate University for Advanced Studies (SOKENDAI)（综合研究大学院大学）
Efficient implementation of the single-reference algebraic diagrammatic construction theory for charged excitations: Applications to the TEMPO radical and DNA base pairs
Third-order algebraic diagrammatic construction theory for electron attachment and ionization energies: Conventional and Green's function implementation
A Low Cost Relativistic Algebraic Diagrammatic Construction Method Based on Cholesky Decomposition and Frozen Natural Spinors for Electronic Ionization, Attachment and Excitation Energy Problem
A generalized exchange-correlation functional: the Neural-Networks approach
A Neural-Networks-based approach is proposed to construct a new type of exchange-correlation functional for density functional theory . It is applied to improve B3LYP functional by taking into account of high-order contributions to the exchange-correlation functional. The improved B3LYP functional is based on a neural network whose structure and synaptic weights are determined from 116 known experimental atomization energies, ionization potentials, proton affinities or total atomic energies which were used by Becke in his pioneer work on the hybrid functionals [J. Chem. Phys. ${\bf 98}$ , 5648…
An assessment of frozen natural orbitals and band gaps using equation of motion coupled cluster theory: a case study on polyacene and trans-polyacetylene
Thermally-assisted-occupation density functional theory with generalized-gradient approximations
我们扩展了最近提出的热辅助占据密度泛函理论（TAO-DFT）[J. - D. Chai，J.Chem.Phys.136，154104（2012）]到广义梯度近似（GGA）交换相关密度泛函。相对于我们之前的TAO-LDA（即，TAO-DFT的局域密度近似），所得TAO-GGA对于广泛的应用，例如热化学、动力学和反应能是显著优越的。对于非共价相互作用，TAO-GGA与经验色散校正显示出优异的性能。由于TAO-LDA和TAO-GGA对具有强静态相关效应的系统的计算效率，它们被应用于研究电子性质（例如，单重态-三重态能隙、垂直电离势、垂直电子亲合势、基本能隙和对称化的冯诺伊曼熵），这对于传统的电子结构方法是非常具有挑战性的。并苯的基态在所有的链长下都是单态。随着并苯长度的增加，单重态-三重态能隙、垂直电离势和基本能隙单调减小，而垂直电子亲合势和对称化冯诺伊曼熵（即，多根特征的度量）单调地增加。
Self-consistent double-hybrid density-functional theory using the optimized-effective-potential method
我们介绍了一个轨道优化的双杂交（DH）计划使用优化有效势（OEP）方法。使用对应于完整的交换相关能量表达式的局部势优化轨道，包括二阶M{\displaystyle M {\math}ller-Plesset（MP2）相关贡献。我们已经实现了一个单参数版本的基于OEP的自洽DH计划使用BLYP密度泛函近似，并将其与相应的非自洽DH计划进行比较，用于计算一些闭壳层原子和分子。虽然基于OEP的自洽性并没有为基态总能量和电离势的计算提供任何改进，但它确实提高了电子亲和势的准确性，并恢复了LUMO轨道能量与中性激发能相关的含义。此外，基于OEP的自洽DH方案提供了相当准确的交换相关势和相关密度。
Delocalization errors in density functional theory are essentially quadratic in fractional occupation number
在实际的密度泛函理论（DFT）中使用的近似泛函偏离了分数电荷精确泛函的分段线性行为。这种偏离导致过量的电荷离域，这导致不正确的密度、分子性质、势垒高度、带隙和激发能。我们提出了一个简单的离域函数来表征这种错误，并发现它几乎是完全线性的分数电子数的系统跨越的大小从H原子的C $_{12}$ H $_{14}$多烯。这导致离域能量误差是分数电子数的二次多项式，这使我们能够通过曲率评估47个流行和最近的泛函的比较性能。二次形式进一步表明，关于单个分数电荷的信息足以消除离域误差的主要来源。因此，将传统的两点信息（如电离势或电子亲合势）概括为第三个基于分数电荷的数据点可以允许拟合/调整具有较低离域误差的泛函。
