具有正确离解极限的经验电荷转移势

Transfer Learned Potential Energy Surfaces: Accurate Anharmonic Vibrational Dynamics and Dissociation Energies for the Formic Acid Monomer and Dimer

The vibrational dynamics of formic acid monomer (FAM) and dimer (FAD) is investigated from machine-learned potential energy surfaces at the MP2 (PES$_{\rm MP2}$) and transfer-learned (PES$_{\rm TL}$) to the CCSD(T) levels of theory. The normal modes and anharmonic frequencies of all modes below 2000 cm$^{-1}$ agree favourably with experiment whereas the OH-stretch mode is challenging for FAM and FAD from normal mode analyses and finite-temperature MD simulations. VPT2 calculations on PES$_{\rm TL}$ for FAM reproduce the experimental OH frequency to within 22 cm$^{-1}$. For FAD the VPT2 calcula…

Yb二聚体离解能、平衡距离和光谱常数的精确计算

Accurate calculations of the dissociation energy, equilibrium distance and spectroscopic constants for the Yb dimer

计算了Yb $_2$分子的$^1Σ_g^+$基态的离解能、平衡距离和光谱常数。相对论效应是通过广义相对论有效实势引入的，具有很高的精度。标量相对论耦合集团方法特别适合于封闭壳层的范德瓦耳斯系统被用于相关处理。广泛的广义相关基集的构造和使用。高阶团簇振幅和自旋轨道相互作用的相对较小的修正被考虑使用较小的基组和自旋轨道密度泛函理论。

Calculation of Ligand Dissociation Energies in Large Transition-Metal Complexes

Despite the importance of ligand dissociation energies for computational chemistry, obtaining accurate ab initio reference data is difficult and density-functional methods of uncertain reliability are chosen for feasibility reasons. Here, we consider advanced coupled-cluster and multi-configurational approaches to reinvestigate our WCCR10 set of ten gas-phase ligand dissociation energies. We assess the potential multi-configurational character of all molecules involved in these reactions in order to determine where single-reference coupled-cluster approaches can be applied. For some reactions …

Well-behaved versus ill-behaved density functionals for single bond dissociation: Separating success from disaster functional by functional for stretched H$_2$

Unrestricted DFT methods are typically expected to describe the homolytic dissociation of nonpolar single bonds in neutral species with qualitative accuracy, due to the lack of significant delocalization error. We however find that many widely used density functional approximations fail to describe features along the dissociation curve of the simple H$_2$ molecule. This is not an universal failure of DFT in the sense that many classic functionals like PBE and B3LYP give very reasonable results, as do some more modern methods like MS2. However, some other widely used functionals like B97-D (emp…

Ab initio study of water dissociation on a charged Pd(111) surface

Interactions between molecules and electrode surfaces play a key role in electrochemical processes and are a subject of extensive research, both experimental and theoretical. In this manuscript, we address the water dissociation reaction on a Pd(111) electrode surface, modelled as a slab embedded in an external electric field. We aim at unraveling the relationship between surface charge and zero-point-energy in aiding or hindering this reaction. We calculate energy barriers with dispersion-corrected density-functional theory and an efficient parallel implementation of the nudged-elastic-band m…

Benchmarking theory with an improved measurement of the ionization and dissociation energies of H$_2$

The dissociation energy of H$_2$ represents a benchmark quantity to test the accuracy of first-principles calculations. We present a new measurement of the energy interval between the EF $^1Σ_g^+(v=0,N=1)$ state and the 54p1$_1$ Rydberg state of H$_2$. When combined with previously determined intervals, this new measurement leads to an improved value of the dissociation energy $D_0^{N=1}$ of ortho-H$_2$ that has, for the first time, reached a level of uncertainty that is three times smaller than the contribution of about 1 MHz resulting from the finite size of the proton. The new result of 359…

Density Functional Theory Based on the Electron Distribution on the Energy Coordinate

We introduced a new electron density n(ε) by projecting the spatial electron density n(r) onto the energy coordinate ε defined with the external potential υ(r) of interest. Then, a density functional theory (DFT) was formulated, where n(ε) serves as a fundamental variable for the electronic energy. It was demonstrated that the Kohn-Sham equation can also be adapted to the DFT that employs the density n(ε) as an argument to the exchange energy functional. An important attribute of the energy density is that it involves the spatially non-local population of the spin-adapted density n(r) at the b…

Systematic study of low energy geometries of copper nano-junctions exposed to water and to species that can result from dissociation of water

A detailed computational analysis has been performed, considering copper atomic contacts that are exposed directly to water molecules, hydroxyl groups, and monatomic as well as molecular hydrogen and oxygen species. The optimized physical bonding structure, electrical conductance and inelastic tunneling spectra (IETS) have been determined theoretically for moderately large structures by performing appropriate ab-initio and semi-empirical calculations. By considering the aforementioned properties, it has been possible to determine that some of the molecular bridging structures may be regarded a…

用系综推广方法消除Kohn-Sham密度泛函理论中的渐近分数解离问题

Elimination of the asymptotic fractional dissociation problem in Kohn-Sham density functional theory using the ensemble-generalization approach

密度泛函理论中的许多近似都错误地预言，多电子系统可以离解成分数电荷碎片。在这里，我们重新审视解离双原子分子的情况下，已知表现出这个问题时，在标准的方法，包括本地自旋密度近似（LSDA）的研究。通过使用我们最近提出的[E。Kraisler和L. Kronik，Phys. Rev. Lett. 110，126403（2013）]整体推广，我们发现，渐近分数解离被消除在所有系统检查，即使潜在的交换相关性（xc）仍然是LSDA。此外，由于系综推广程序，Kohn-Sham势发展的空间步骤之间的解离原子，反映了出现的衍生物的xc能量泛函的不连续性。这一步，在过去预测的精确科恩-沙姆潜力和观察到的一些更先进的近似形式，是一个理想的功能，防止任何分数之间的电荷转移系统的片段。人们通常认为，简单的xc近似，如LSDA不能发展这一步。然而，我们的研究结果表明，集成推广到分数电子密度自动引入所需的步骤，甚至最简单的近似xc泛函和正确预测渐近整数离解。

QTPIE：具有极化电流均衡的电荷转移。具有正确渐近性的涨落电荷模型

QTPIE: Charge Transfer with Polarization Current Equalization. A fluctuating charge model with correct asymptotics

极化和电荷转移是很难用常规力场描述的重要效应。电荷平衡模型可以在大规模分子模拟中包括这两种效应。然而，当键断裂时，这些模型的行为不正确，使得难以在反作用力场的上下文中使用它们。本文提出了一种描述分子中电荷流的新方法--量子点积分方程（QTPIE）。QTPIE方法基于电荷转移变量（与原子电荷相反），并正确处理解离附近的渐近行为。它也能够提供一个现实的描述面内极化率。

非线性且非经验的双杂化密度泛函

Non-linear and non-empirical double hybrid density functional

本文提出无拟合参数的非线性非经验双杂化泛函 nlane-SCAN，通过绝热连接插值统一弱关联与完全相互作用极限，在能量、反应、非共价作用及键解离等基准上显著提升预测精度。

使用轨道无关泛函建模分子解离的 Kohn-Sham 势：原理验证

Modelling the Kohn-Sham potential for molecular dissociation with orbital-independent functionals: a proof of principle

提出一种基于精确因子分解和严格关联电子极限的轨道无关 Kohn-Sham 势建模策略，并在拉伸异核分子模型中验证其可重现精确势阶跃。

通过 PZ-SIC 框架使用自相互作用校正的 SCAN 密度与轨道改进 XYG3 型双杂化近似：xDH@SCAN(SIC) 方法

Improving XYG3-type Doubly Hybrid Approximation using Self-Interaction Corrected SCAN Density and Orbitals via the PZ-SIC Framework: the xDH@SCAN(SIC) Approach

针对 xDH 方法在分子解离极限下因密度误差导致的局限性，提出使用 PZ-SIC 方案校正的 SCAN 密度和轨道的 5 参数 xDH@SCAN(SIC) 方法，在多种挑战性系统中实现了平衡且准确的描述。

O$_3$的高能反应动力学

High-Energy Reaction Dynamics of O$_3$

本文基于新势能面利用准经典轨迹和神经网络模型研究O$_3$高能交换与解离反应动力学，重现负温度依赖性并预测产物态分布。

基于分割密度泛函理论的强电子关联

Strong Electron Correlation from Partition Density Functional Theory

针对 KS-DFT 在强关联电子系统中误差大的问题，提出基于分割密度泛函理论的广义重叠近似（GOA）方法，有效改进了氢链解离曲线与电子密度，且无需破坏自旋对称性。

超越随机相位近似的静态关联：用Bethe-Salpeter方程和含时GW解离H2

Static correlation beyond the random phase approximation: Dissociating H2 with the Bethe-Salpeter equation and time-dependent GW

我们研究了H $_2$分子在解离极限下的相关能的各种近似，其中基态很难用单一的斯莱特行列式来描述。的相关能来自密度响应函数，它表明，响应函数来自Hedin方程（随机相位近似（RPA），时间依赖Hartree-Fock（TDHF），Bethe-Salpeter方程（BSE），和时间依赖GW（TDGW））都再现正确的解离极限。我们还表明，BSE提高了RPA和TDHF内获得的相关能量显着的中间结合距离。二聚体的哈伯德模型使我们能够获得精确的分析结果的各种近似，这是很容易与精确的对角化模型相比。此外，该模型被证明重现所有的定性结果从\textit{ab initio}计算，并证实，BSE大大提高了RPA和TDHF的结果，尽管事实上，BSE激发光谱分解的解离极限。相比之下，二阶屏蔽交换（SOSEX）给出了一个贫穷的描述解离极限，这可以归因于它不能从一个不可约的响应函数的事实。

Empirical corrections and pair interaction energies in the fragment molecular orbital method

The energy and analytic gradient are developed for FMO combined with the Hartree-Fock method augmented with three empirical corrections (HF-3c). The auxiliary basis set approach to FMO is extended to perform pair interaction energy decomposition analysis. The FMO accuracy is evaluated for several typical systems including 3 proteins. Pair interaction energies computed with different approaches in FMO are compared for a water cluster and protein-ligand complexes.

Self-consistent calculation of localized orbital scaling correction for correct electron densities and energy level alignment in density functional theory

The recently developed localized orbital scaling correction (LOSC) method shows the ability to systematically and size-consistently reduce the delocalization error existing in conventional density functional approximations (DFAs). Applying LOSC to conventional DFAs (LOSC-DFAs) gives much improvement for the description of related properties, including band gaps, total energies and photoemission spectra. However, concern and issue remain: the application of LOSC to DFAs is mainly through a post self-consistent field (SCF) manner, and few results from applying LOSC to DFAs with a SCF manner have…

密度泛函理论的不连续性

Integer Discontinuity of Density Functional Theory

Kohn-Sham理论的交换相关能的密度泛函近似，如局域密度近似和广义梯度近似，缺乏众所周知的整数不连续性，这是正确描述分子解离的关键特征。此外，当电子数是从巨正则系综统计得到的非整数时，交换相关能的标准近似也不能得到基态能量与电子数的正确线性关系。我们提出了一个正式的框架来恢复任何密度泛函近似的整数不连续性。我们的形式主义来自一个公式的确切的能量泛函和一个新的约束搜索功能，恢复的线性依赖的能量上的电子数。

电荷调节相互作用的场论描述

Field theoretic description of charge regulation interaction

为了找到两个具有可解离电荷基团的蛋白质在水溶液中静电相互作用的确切形式，我们研究了由两个具有电荷解离位点的宏观表面浸入仅反离子溶液中组成的模型系统。在平均场近似下，导出了巨正则配分函数的场论表示，给出了具有Ninham-Parsegian边界条件的Poisson-Boltzmann理论.平均场周围的高斯起伏，然后分析在最低阶的校正，我们计算的解析和准确的，使用路径积分表示的配分函数的谐振子与时间相关的频率。一阶（一个回路）自由能校正给出了在适当的限度内降低到零频率范德华形式的相互作用自由能，但通常由于解离位点处的电荷波动而产生单极波动项。我们的提法开辟了可能性，调查柯克伍德-舒梅克相互作用在更一般的情况下，他们原来的推导失败。

带完全重正化和微扰三重激发校正的相对论耦合簇方法

Relativistic coupled cluster with completely renormalized and perturbative triples corrections

本研究在1eX2C相对论框架下实现CCSD的非迭代三重激发校正，通过铜、银、金二聚体计算验证方法有效性，明确自旋-轨道耦合、三重激发关联及相对论效应等对相关体系性质的影响。

双态Li ${}_3$的长程三体原子-硅藻势

Long-range three-body atom-diatom potential for doublet Li${}_3$

用全电子RCCSD（T）方法在冻结硅藻近似下计算了${}^2A'$锂三聚体基态的长程{ \em ab initio}势能面. { \em ab initio}能量校正基组叠加误差，并外推到完整的基础限制。分子的范德华色散系数和三体色散阻尼项的原子-双原子解离极限的线性最小二乘法拟合，并示出是一个基本上精确的表示{ \em从头算}表面在大范围内。

Critical analysis of radical scavenging properties of atorvastatin in methanol recently estimated via density functional theory

In this communication we draw attention on serious flaws that plague recently reported antioxidant properties of atorvastatin (ATV) in methanol. First and foremost, we emphasize that the O-H bond dissociation energies (BDE) of about 400\,kcal/mol previously reported are completely wrong. Further, we present results refuting the previous claim that the proton affinity (PA) of ATV is smaller than that of the ascorbic acid. That unfounded claim relies on incorrect data for PA's ascorbic acid (which we correct here) circulated in the literature. Further, we correct the values of the chemical react…

含时交换关联势不连续性的物理特征

Physical signatures of discontinuities of the time-dependent exchange-correlation potential

含时密度泛函理论（TDDFT）中的精确交换关联势（XC势）在空间受限区域或孤立子系统中随着粒子数的变化会产生台阶和不连续性。我们证明了自相互作用校正的绝热局域密度近似的XC势具有这种性质，使用的例子中的电子损失的模型量子阱系统。然后，我们研究的XC势的不连续性的非对称双量子阱系统的解离过程的实时模拟的影响，并表明，它显着地影响所产生的孤立的单量子阱的人口。这表明了在电离、离解或电荷转移过程的TDDFT描述中适当考虑不连续性的重要性。

Reducing charge delocalization error of density functional theory

The charge delocalization error, besides nondynamic correlation, has been a major challenge to density functional theory. Contemporary functionals undershoot the dissociation of symmetric charged dimers A2+, a simple but stringent test, predict a spurious barrier and improperly delocalize charges for charged molecular clusters. We extend a functional designed for nondynamic correlation to treat the charge delocalization error by modifying the nondynamic correlation for parallel spins. The modified functional eliminates those problems and reduces the multielectron self-interaction error. Furthe…

Localized Orbital Scaling Correction for Systematic Elimination of Delocalization Error in Density Functional Approximations

The delocalization error of popular density functional approximations (DFAs) leads to diversified problems in present-day density functional theory calculations. For achieving a universal elimination of delocalization error, we develop a localized orbital scaling correction (LOSC) framework, which unifies our previously proposed global and local scaling approaches. The LOSC framework accurately characterizes the distributions of global and local fractional electrons, and is thus capable of correcting system energy, energy derivative and electron density in a self-consistent and size-consistent…

氢化铍（BeH）：经过86年的光谱学研究，我们现在在哪里

Beryllium monohydride (BeH): Where we are now, after 86 years of spectroscopy

BeH是从头算方法和研究Born-Oppenheimer击穿的最重要的基准体系之一。然而，迄今为止，基态电子态的最佳经验势和最佳从头算势在远距离区域给出了截然不同的预测，在远距离区域之外进行了测量，对于^{9} BeH，远距离区域大约为\sim 1000 cm ^{-1}，对于^{9} BeD，远距离区域大约为\sim 3000 cm ^{-1}，对于^{9} BeT，远距离区域大约为\sim 13000 cm^{-1}。改进的经验势和Born-Oppenheimer击穿修正现在已经建立了所有三个同位素的基态电子态X（1^{2}<$^{+}）。由新的经验势预测的^{9} BeH的离解能现在更接近于当前最好的从头计算预测，后者与先前最好的经验势之间的差异超过66%。先前最好的经验势预测了所有三种同位素的未观察到的振动能级的存在，目前最好的从头算研究也预测了所有这些能级的存在，还有四个。目前的经验势同意所有这些额外的水平，而不是由早期的经验势预测的从头计算预测。除了一个例外，所有已经测量过的振动能级之间的能隙都被预测为新的经验势和目前最好的从头算势之间的一致性优于1 cm^{-1}，但是对于未观测到的能级的一些预测仍然存在很大的分歧，并且平衡键长相差了几个数量级。