updated manuscript

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Emmanuel Giner 2019-04-10 23:42:46 +02:00
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\begin{abstract}
We report a universal density-based basis-set incompleteness correction that can be applied to any wave-function method while keeping the correct limit when reaching the complete basis set (CBS).
The present correction relies on a short-range correlation density functional (with multi-determinant reference) from range-separated density-functional theory (RS-DFT) to estimate the basis-set incompleteness error.
Contrary to conventional RS-DFT schemes which require an \textit{ad hoc} range-separation \textit{parameter} $\mu$, the key ingredient here is a range-separation \textit{function} $\mu(\bf{r})$ which automatically adapts to the basis-set and accounts for the non-homogeneity of the incompleteness error in real space.
Contrary to conventional RS-DFT schemes which require an \textit{ad hoc} range-separation \textit{parameter} $\mu$, the key ingredient here is a range-separation \textit{function} $\mu(\bf{r})$ which automatically adapts to the basis-set used in a wave-function calculation and accounts for the non-homogeneity of the incompleteness error in real space.
As illustrative examples, we show how this density-based correction allows us to obtain CCSD(T) atomization energies near the CBS limit for the G2-1 set of molecules with compact Gaussian basis sets.
For example, our basis-set corrected CCSD(T)+LDA/cc-pVTZ and CCSD(T)+PBE/cc-pVTZ methods return mean absolute deviations of 2.89 and 2.46 kcal/mol, respectively, compared to CCSD(T)/CBS atomization energies, while these values drop below 1 {\kcal} with cc-pVQZ.
For example, while the CCSD(T)/cc-pVTZ model shows a mean deviation of 7.79 kcal/mol compared to CCSD(T)/CBS atomization energies, our basis-set corrected CCSD(T)+LDA and CCSD(T)+PBE methods performed in the same basis return 2.89 and 2.46 kcal/mol, respectively, while these values drop below 1 {\kcal} with the cc-pVQZ basis set.
\end{abstract}
\maketitle