Semiempirical GGA-type density functional constructed with a long-range dispersion correction
Semiempirical GGA-type density functional constructed with a long-range dispersion correction
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DOI：
10.1002/jcc.20495
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发表时间：
2006-11-30
影响因子：
3
通讯作者：
Grimme, Stefan
中科院分区：
文献类型：
--
作者：
Grimme, Stefan
提出了一种新的广义梯度近似（GGA）型密度泛函（DF）B 97-D。它基于1997年Becke的幂级数模型，并通过包括C-6形式的阻尼原子成对色散修正来明确参数化。R-6在此校正中使用的参数的一般计算方案已被建立和氙的元素的参数和几个常见的密度泛函（BLYP，PBE，TPSS，B3 LYP）的色散部分的比例因子的报告。新的功能进行测试，与其他GGA和B3 LYP混合功能的标准热化学基准集相比，40个非共价键结合的复合物，包括大型堆叠的芳香族分子和第11族元素簇，并计算分子的几何形状。进一步的交叉验证测试进行了有机金属反应和标准泛函的其他困难的问题。总之，发现B 97-D属于最精确的通用GGA之一，例如对于G97/2组的形成热，平均绝对偏差仅为3.8 kcal mol（-1）。对于包括许多纯货车德瓦耳斯配合物的非共价键结合系统，性能异常良好，达到CCSD（T）的平均精度。发展的基本策略是将密度泛函描述限制在较短的电子相关长度尺度上，并通过阻尼C-6来描述中到大原子间距离的情况。R-6术语似乎是非常成功的，正如一些众所周知的困难反应所证明的那样。例如，对于较大的支链烷烃到直链烷烃的异构化，B 97-D是唯一可用的DF，其产生能量差的正确符号。从实用的角度来看，新的功能似乎是相当强大的，因此建议作为一个有效的和准确的量子化学方法的大型系统的色散力是普遍的重要性。(C)2006 Wiley Periodicals，Inc.
A new density functional (DF) of the generalized gradient approximation (GGA) type for general chemistry applications termed B97-D is proposed. It is based on Becke's power-series ansatz from 1997 and is explicitly parameterized by including damped atom-pairwise dispersion corrections of the form C-6 . R-6. A general computational scheme for the parameters used in this correction has been established and parameters for elements up to xenon and a scaling factor for the dispersion part for several common density functionals (BLYP, PBE, TPSS, B3LYP) are reported. The new functional is tested in comparison with other GGAs and the B3LYP hybrid functional on standard thermochemical benchmark sets, for 40 noncovalently bound complexes, including large stacked aromatic molecules and group 11 element clusters, and for the computation of molecular geometries. Further cross-validation tests were performed for organometallic reactions and other difficult problems for standard functionals. In summary, it is found that B97-D belongs to one of the most accurate general purpose GGAs, reaching, for example for the G97/2 set of heat of formations, a mean absolute deviation of only 3.8 kcal mol(-1). The performance for noncovalently bound systems including many pure van der Waals complexes is exceptionally good, reaching on the average CCSD(T) accuracy. The basic strategy in the development to restrict the density functional description to shorter electron correlation lengths scales and to describe situations with medium to large interatomic distances by damped C-6 . R-6 terms seems to be very successful, as demonstrated for some notoriously difficult reactions. As an example, for the isomerization of larger branched to linear alkanes, B97-D is the only DF available that yields the right sign for the energy difference. From a practical point of view, the new functional seems to be quite robust and it is thus suggested as an efficient and accurate quantum chemical method for large systems where dispersion forces are of general importance. (C) 2006 Wiley Periodicals, Inc.