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。
英文摘要:
We introduce an orbital-optimized double-hybrid (DH) scheme using the optimized-effective-potential (OEP) method. The orbitals are optimized using a local potential corresponding to the complete exchange-correlation energy expression including the second-order M{ø}ller-Plesset (MP2) correlation contribution. We have implemented a one-parameter version of this OEP-based self-consistent DH scheme using the BLYP density-functional approximation and compared it to the corresponding non-self-consistent DH scheme for calculations on a few closed-shell atoms and molecules. While the OEP-based self-consistency does not provide any improvement for the calculations of ground-state total energies and ionization potentials, it does improve the accuracy of electron affinities and restores the meaning of the LUMO orbital energy as being connected to a neutral excitation energy. Moreover, the OEP-based self-consistent DH scheme provides reasonably accurate exchange-correlation potentials and correlated densities.
Faster Exact Exchange for Solids via occ-RI-K: Application to Combinatorially Optimized Range-Separated Hybrid Functionals for Simple Solids with Pseudopotentials Near the Basis Set Limit
In this work, we developed and showcased the occ-RI-K algorithm to compute the exact exchange contribution in density functional calculations of solids near the basis set limit. Within the gaussian planewave (GPW) density fitting, our algorithm achieves a 1-2 orders of magnitude speedup compared to conventional GPW algorithms. Since our algorithm is well-suited for simulations with large basis sets, we applied it to 12 hybrid density functionals with pseudopotentials and a large uncontracted basis set to assess their performance on band gaps of 25 simple solids near the basis set limit. The la…
Time-dependent optimized coupled-cluster method with doubles and perturbative triples [TD-OCCD(T)] for first principles simulation of multielectron dynamics
Empirical Double-Hybrid Density Functional Theory: A 'Third Way' In Between WFT and DFT
双杂化密度泛函理论可以说位于波函数方法和DFT之间的接缝处:它代表了John P. Perdew的“雅各布斯阶梯”上的第5阶的特殊情况。对于大的和化学上不同的基准,如GMTKN 55,经验的双混合泛函与色散校正可以实现接近波函数方法的精度在成本没有很大不同的混合DFT方法,提供RI-MP2和/或其他MP2加速技术可在电子结构代码。只需要六个或更少的经验参数。对于振动频率,可以实现CCSD和CCSD(T)之间的中间精度,并且其他属性的性能也令人鼓舞。同样,只要静态相关性不太强,有机物反应也可以很好地处理。进一步的前景进行了讨论,包括范围分离和RPA为基础的方法。
xDH double hybrid functionals can be qualitatively incorrect for non-equilibrium geometries: Dipole moment inversion and barriers to radical-radical association using XYG3 and XYGJ-OS
Electronic structure and optical properties of halide double perovskites from a Wannier-localized optimally-tuned screened range-separated hybrid functional