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\affiliation{\LCT}
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\begin{abstract}
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%\begin{wrapfigure}[12]{o}[-1.2cm]{0.4\linewidth}
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% \centering
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% \includegraphics[width=\linewidth]{TOC}
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%\end{wrapfigure}
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We report a universal density-based basis set incompleteness correction that can be applied to any wave function method.
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The present correction, which appropriately vanishes in the complete basis set (CBS) limit, relies on short-range correlation density functionals (with multi-determinant reference) from range-separated density-functional theory (RS-DFT) to estimate the basis set incompleteness error.
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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 spatial non-homogeneity of the basis set incompleteness error.
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\label{tab:diatomics}
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Frozen-core atomization energies (in {\kcal}) of \ce{C2}, \ce{O2}, \ce{N2} and \ce{F2} computed with various methods and basis sets.
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The deviations with respect to the corresponding CBS values are reported in parenthesis.
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See main text for more details.
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}
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\begin{ruledtabular}
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\begin{tabular}{llddddd}
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\begin{table}
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\caption{
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\label{tab:AE}
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Deviation from the reference CBS atomization energies (in {\kcal}) for various methods and basis sets.}
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Deviation from the reference CCSD(T)/CBS atomization energies (in {\kcal}) for various methods and basis sets.
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See main text for more details.}
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\begin{ruledtabular}
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\begin{tabular}{lddddddddddd}
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&
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& \tabc{cc-pVDZ} & \tabc{cc-pVTZ} & \tabc{cc-pVQZ}
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& \tabc{cc-pVDZ} & \tabc{cc-pVTZ} & \tabc{cc-pVQZ}
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\\
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\hline
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\ce{BeH} & 50.12 & -4.87 & -1.52 & -0.40 & -0.19 & -2.24 & -0.54 & 0.\times 10^{-2} & -2.24 & -0.54 & 0.00 \\
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\ce{C2H2} & 403.00 & -33.08 & -9.89 & -3.64 & -1.76 & -15.21 & -2.27 & 0.16 & -15.21 & -2.27 & 0.16 \\
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\ce{C2H4} & 561.69 & -36.58 & -10.70 & -3.87 & -1.84 & -14.30 & -1.82 & 0.30 & -14.30 & -1.82 & 0.30 \\
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\ce{C2H6} & 710.81 & -41.69 & -11.64 & -4.19 & -2.03 & -14.35 & -1.19 & 0.54 & -14.35 & -1.19 & 0.54 \\
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\ce{CH} & 83.89 & -8.39 & -2.42 & -0.86 & -0.39 & -3.24 & -0.48 & 0.05 & -3.24 & -0.48 & 0.05 \\
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\ce{CH2 $^1A_1$} & 180.61 & -15.23 & -4.29 & -1.51 & -0.68 & -5.80 & -0.72 & 0.12 & -5.80 & -0.72 & 0.12 \\
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\ce{CH2 $^3B_1$} & 189.94 & -12.60 & -3.25 & -1.11 & -0.51 & -5.65 & -0.86 & -0.12 & -5.65 & -0.86 & -0.12 \\
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\ce{CH3} & 306.81 & -19.55 & -5.08 & -1.77 & -0.83 & -7.54 & -0.69 & 0.12 & -7.54 & -0.69 & 0.12 \\
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\ce{CH3Cl} & 395.02 & -29.15 & -9.70 & -3.83 & -1.72 & -12.76 & -2.96 & -0.64 & -12.76 & -2.96 & -0.64 \\
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\ce{CH4} & 419.19 & -23.97 & -6.19 & -2.14 & -1.03 & -8.17 & -0.37 & 0.38 & -8.17 & -0.37 & 0.38 \\
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\ce{CN} & 179.32 & -21.44 & -8.55 & -3.30 & -1.63 & -8.63 & -2.11 & 0.09 & -8.63 & -2.11 & 0.09 \\
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\ce{CO} & 258.64 & -17.46 & -7.01 & -2.62 & -1.33 & -7.38 & -1.69 & 0.42 & -7.38 & -1.69 & 0.42 \\
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\ce{CO2} & 388.29 & -32.10 & -12.54 & -4.75 & -2.39 & -14.50 & -3.28 & 0.52 & -14.50 & -3.28 & 0.52 \\
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\ce{CS} & 170.82 & -17.82 & -8.45 & -3.71 & -1.47 & -9.04 & -3.78 & -1.0 & -9.04 & -3.78 & -1.0 \\
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\ce{Cl2} & 59.33 & -17.79 & -7.18 & -3.39 & -1.28 & -13.16 & -4.41 & -1.80 & -13.16 & -4.41 & -1.80 \\
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\ce{ClF} & 62.43 & -20.00 & -7.36 & -3.18 & -1.19 & -15.52 & -4.76 & -1.66 & -15.52 & -4.76 & -1.66 \\
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\ce{ClO} & 64.35 & -23.33 & -8.68 & -4.09 & -1.62 & -17.46 & -5.40 & -2.19 & -17.46 & -5.40 & -2.19 \\
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\ce{F2} & 38.24 & -12.53 & -3.70 & -1.76 & -0.88 & -9.09 & -1.72 & -0.52 & -9.09 & -1.72 & -0.52 \\
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\ce{H2CO} & 373.18 & -28.21 & -9.53 & -3.55 & -1.70 & -11.74 & -2.16 & 0.26 & -11.74 & -2.16 & 0.26 \\
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\ce{H2O} & 232.78 & -23.97 & -7.67 & -2.85 & -1.21 & -12.79 & -2.92 & -0.62 & -12.79 & -2.92 & -0.62 \\
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\ce{H2O2} & 268.77 & -33.22 & -10.75 & -4.37 & -2.09 & -17.09 & -3.37 & -0.59 & -17.09 & -3.37 & -0.59 \\
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\ce{H2S} & 183.36 & -16.42 & -6.09 & -2.26 & -0.79 & -8.26 & -2.91 & -0.83 & -8.26 & -2.91 & -0.83 \\
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\ce{H3COH} & 512.25 & -39.65 & -12.16 & -4.52 & -2.10 & -17.28 & -2.93 & -0.1 & -17.28 & -2.93 & -0.1 \\
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\ce{H3CSH} & 473.92 & -36.54 & -12.24 & -4.71 & -1.98 & -16.19 & -4.00 & -0.85 & -16.19 & -4.00 & -0.85 \\
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\ce{HCN} & 311.54 & -29.08 & -10.32 & -3.95 & -1.95 & -11.81 & -2.11 & 0.22 & -11.81 & -2.11 & 0.22 \\
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\ce{HCO} & 277.92 & -22.87 & -8.28 & -3.06 & -1.46 & -10.20 & -2.31 & 0.16 & -10.20 & -2.31 & 0.16 \\
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\ce{HCl} & 107.31 & -9.11 & -3.37 & -1.31 & -0.48 & -4.84 & -1.73 & -0.60 & -4.84 & -1.73 & -0.60 \\
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\ce{HF} & 141.67 & -15.33 & -4.73 & -1.72 & -0.73 & -9.59 & -2.21 & -0.53 & -9.59 & -2.21 & -0.53 \\
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\ce{HOCl} & 165.85 & -27.19 & -9.45 & -4.05 & -1.68 & -16.76 & -4.40 & -1.38 & -16.76 & -4.40 & -1.38 \\
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\ce{Li2} & 24.10 & -1.64 & -0.37 & -0.08 & -0.04 & -0.47 & 0.05 & 0.09 & -0.47 & 0.05 & 0.09 \\
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\ce{LiF} & 138.33 & -15.98 & -6.20 & -2.02 & -1.0 & -8.50 & -2.56 & -0.06 & -8.50 & -2.56 & -0.06 \\
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\ce{LiH} & 57.70 & -5.80 & -1.34 & -0.43 & -0.20 & -2.36 & -0.16 & 0.07 & -2.36 & -0.16 & 0.07 \\
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\ce{N2} & 227.18 & -27.25 & -10.85 & -4.40 & -2.15 & -10.85 & -2.34 & -0.\times 10^{-2} & -10.85 & -2.34 & 0.00 \\
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\ce{N2H4} & 437.39 & -50.52 & -16.80 & -6.47 & -2.99 & -21.69 & -4.16 & -0.66 & -21.69 & -4.16 & -0.66 \\
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\ce{NH} & 82.86 & -11.49 & -3.67 & -1.40 & -0.63 & -4.91 & -0.87 & -0.23 & -4.91 & -0.87 & -0.23 \\
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\ce{NH2} & 182.14 & -21.58 & -6.83 & -2.59 & -1.16 & -9.43 & -1.72 & -0.36 & -9.43 & -1.72 & -0.36 \\
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\ce{NH3} & 297.46 & -30.02 & -9.32 & -3.49 & -1.54 & -13.23 & -2.33 & -0.41 & -13.23 & -2.33 & -0.41 \\
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\ce{NO} & 151.73 & -20.13 & -8.33 & -3.40 & -1.66 & -8.46 & -2.18 & -0.07 & -8.46 & -2.18 & -0.07 \\
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\ce{Na2} & 16.44 & -1.14 & -0.21 & -0.11 & -0.03 & -0.22 & 0.08 & 0.02 & -0.22 & 0.08 & 0.02 \\
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\ce{NaCl} & 99.61 & -13.83 & -6.33 & -2.63 & -1.16 & -6.70 & -3.05 & -0.88 & -6.70 & -3.05 & -0.88 \\
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\ce{O2} & 119.64 & -15.78 & -6.09 & -2.52 & -1.23 & -9.00 & -2.47 & -0.41 & -9.00 & -2.47 & -0.41 \\
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\ce{OH} & 107.08 & -12.86 & -4.17 & -1.57 & -0.69 & -6.71 & -1.54 & -0.30 & -6.71 & -1.54 & -0.30 \\
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\ce{P2} & 115.68 & -26.99 & -12.04 & -5.02 & -2.05 & -12.90 & -4.59 & -0.77 & -12.90 & -4.59 & -0.77 \\
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\ce{PH2} & 153.91 & -16.69 & -5.87 & -2.08 & -0.77 & -7.75 & -2.37 & -0.42 & -7.75 & -2.37 & -0.42 \\
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\ce{PH3} & 241.49 & -22.83 & -8.02 & -2.88 & -1.04 & -10.51 & -3.25 & -0.65 & -10.51 & -3.25 & -0.65 \\
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\ce{S2} & 103.07 & -21.55 & -9.78 & -4.44 & -1.68 & -14.48 & -5.62 & -2.11 & -14.48 & -5.62 & -2.11 \\
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\ce{SO} & 125.12 & -29.67 & -10.55 & -4.65 & -1.51 & -22.23 & -6.51 & -2.30 & -22.23 & -6.51 & -2.30 \\
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\ce{SO2} & 258.09 & -72.08 & -25.99 & -11.66 & -3.46 & -54.88 & -16.77 & -6.22 & -54.88 & -16.77 & -6.22 \\
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\ce{Si2} & 75.74 & -14.79 & -5.51 & -2.25 & -0.93 & -8.98 & -2.52 & -0.60 & -8.98 & -2.52 & -0.60 \\
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\ce{Si2H6} & 535.58 & -42.77 & -14.82 & -5.05 & -1.77 & -21.04 & -6.55 & -1.29 & -21.04 & -6.55 & -1.29 \\
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\ce{SiH2 $^1A_1$} & 153.66 & -13.20 & -4.29 & -1.47 & -0.50 & -7.98 & -2.76 & -0.83 & -7.98 & -2.76 & -0.83 \\
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\ce{SiH2 $^3B_1$} & 133.17 & -11.32 & -3.83 & -1.15 & -0.37 & -7.66 & -3.01 & -0.91 & -7.66 & -3.01 & -0.91 \\
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\ce{SiH3} & 227.99 & -17.54 & -5.85 & -1.82 & -0.59 & -8.83 & -2.88 & -0.56 & -8.83 & -2.88 & -0.56 \\
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\ce{SiH4} & 324.59 & -23.03 & -7.65 & -2.44 & -0.78 & -10.85 & -3.35 & -0.58 & -10.85 & -3.35 & -0.58 \\
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\ce{SiO} & 191.48 & -31.12 & -10.81 & -4.45 & -1.61 & -20.54 & -5.27 & -1.19 & -20.54 & -5.27 & -1.19 \\
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\hline
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\ce{BeH} & 50.12 & -3.38 & -1.01 & -0.36 & -0.19 & -0.75 & -0.03 & 0.04 & -0.75 & -0.03 & 0.04 \\
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\ce{C2H2} & 403.00 & -22.99 & -8.69 & -3.43 & -1.76 & -5.12 & -1.08 & 0.37 & -5.12 & -1.08 & 0.37 \\
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\ce{C2H4} & 561.69 & -27.16 & -9.44 & -3.59 & -1.84 & -4.88 & -0.56 & 0.58 & -4.88 & -0.56 & 0.58 \\
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\ce{C2H6} & 710.81 & -32.62 & -10.65 & -3.97 & -2.03 & -5.28 & -0.20 & 0.76 & -5.28 & -0.20 & 0.76 \\
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\ce{CH} & 83.89 & -5.96 & -1.97 & -0.75 & -0.39 & -0.81 & -0.03 & 0.15 & -0.81 & -0.03 & 0.15 \\
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\ce{CH2 ^1A_1} & 180.61 & -10.99 & -3.57 & -1.34 & -0.68 & -1.55 & 0.00 & 0.29 & -1.55 & 0.00 & 0.29 \\
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\ce{CH2 ^3B_1} & 189.94 & -8.82 & -2.78 & -1.0 & -0.51 & -1.87 & -0.38 & 0.00 & -1.87 & -0.38 & -0.00 \\
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\ce{CH3} & 306.81 & -14.33 & -4.47 & -1.62 & -0.83 & -2.33 & -0.08 & 0.27 & -2.33 & -0.08 & 0.27 \\
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\ce{CH3Cl} & 395.02 & -20.77 & -8.34 & -3.35 & -1.72 & -4.38 & -1.60 & -0.16 & -4.38 & -1.60 & -0.16 \\
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\ce{CH4} & 419.19 & -18.35 & -5.64 & -2.01 & -1.03 & -2.55 & 0.18 & 0.51 & -2.55 & 0.18 & 0.51 \\
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\ce{CN} & 179.32 & -14.98 & -7.26 & -3.18 & -1.63 & -2.16 & -0.82 & 0.20 & -2.16 & -0.82 & 0.20 \\
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\ce{CO} & 258.64 & -11.01 & -5.94 & -2.60 & -1.33 & -0.93 & -0.61 & 0.44 & -0.93 & -0.61 & 0.44 \\
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\ce{CO2} & 388.29 & -20.79 & -10.95 & -4.67 & -2.39 & -3.19 & -1.69 & 0.60 & -3.19 & -1.69 & 0.60 \\
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\ce{CS} & 170.82 & -10.72 & -6.25 & -2.88 & -1.47 & -1.94 & -1.58 & -0.16 & -1.94 & -1.58 & -0.16 \\
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\ce{Cl2} & 59.33 & -8.26 & -5.23 & -2.49 & -1.28 & -3.63 & -2.46 & -0.90 & -3.63 & -2.46 & -0.90 \\
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\ce{ClF} & 62.43 & -8.51 & -4.83 & -2.33 & -1.19 & -4.02 & -2.23 & -0.81 & -4.02 & -2.23 & -0.81 \\
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\ce{ClO} & 64.35 & -11.86 & -6.35 & -3.16 & -1.62 & -5.99 & -3.08 & -1.25 & -5.99 & -3.08 & -1.25 \\
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\ce{F2} & 38.24 & -6.62 & -3.52 & -1.72 & -0.88 & -3.17 & -1.54 & -0.48 & -3.17 & -1.54 & -0.48 \\
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\ce{H2CO} & 373.18 & -19.31 & -8.07 & -3.31 & -1.70 & -2.84 & -0.70 & 0.50 & -2.84 & -0.70 & 0.50 \\
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\ce{H2O} & 232.78 & -15.21 & -5.83 & -2.37 & -1.21 & -4.03 & -1.07 & -0.14 & -4.03 & -1.07 & -0.14 \\
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\ce{H2O2} & 268.77 & -22.78 & -9.44 & -4.08 & -2.09 & -6.64 & -2.06 & -0.30 & -6.64 & -2.06 & -0.30 \\
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\ce{H2S} & 183.36 & -10.66 & -4.33 & -1.55 & -0.79 & -2.50 & -1.16 & -0.12 & -2.50 & -1.16 & -0.12 \\
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\ce{H3COH} & 512.25 & -28.32 & -10.40 & -4.10 & -2.10 & -5.95 & -1.17 & 0.31 & -5.95 & -1.17 & 0.31 \\
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\ce{H3CSH} & 473.92 & -25.84 & -10.02 & -3.88 & -1.98 & -5.49 & -1.79 & -0.01 & -5.49 & -1.79 & -0.01 \\
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\ce{HCN} & 311.54 & -20.86 & -9.06 & -3.80 & -1.95 & -3.59 & -0.85 & 0.37 & -3.59 & -0.85 & 0.37 \\
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\ce{HCO} & 277.92 & -15.04 & -6.87 & -2.84 & -1.46 & -2.38 & -0.89 & 0.37 & -2.38 & -0.89 & 0.37 \\
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\ce{HCl} & 107.31 & -5.64 & -2.46 & -0.93 & -0.48 & -1.37 & -0.81 & -0.22 & -1.37 & -0.81 & -0.22 \\
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\ce{HF} & 141.67 & -8.45 & -3.48 & -1.42 & -0.73 & -2.70 & -0.96 & -0.23 & -2.70 & -0.96 & -0.23 \\
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\ce{HOCl} & 165.85 & -15.82 & -7.34 & -3.28 & -1.68 & -5.39 & -2.29 & -0.62 & -5.39 & -2.29 & -0.62 \\
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\ce{Li2} & 24.10 & -0.78 & -0.30 & -0.07 & -0.04 & 0.39 & 0.13 & 0.1 & 0.39 & 0.13 & 0.1 \\
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\ce{LiF} & 138.33 & -10.78 & -4.56 & -1.95 & -1.0 & -3.30 & -0.91 & 0.02 & -3.30 & -0.91 & 0.02 \\
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\ce{LiH} & 57.70 & -4.15 & -1.05 & -0.38 & -0.20 & -0.71 & 0.12 & 0.11 & -0.71 & 0.12 & 0.11 \\
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\ce{N2} & 227.18 & -18.66 & -9.41 & -4.20 & -2.15 & -2.26 & -0.90 & 0.20 & -2.26 & -0.90 & 0.20 \\
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\ce{N2H4} & 437.39 & -36.95 & -14.25 & -5.83 & -2.99 & -8.13 & -1.60 & -0.01 & -8.13 & -1.60 & -0.01 \\
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\ce{NH} & 82.86 & -8.10 & -3.02 & -1.24 & -0.63 & -1.51 & -0.22 & -0.06 & -1.51 & -0.22 & -0.06 \\
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\ce{NH2} & 182.14 & -15.31 & -5.61 & -2.26 & -1.16 & -3.16 & -0.50 & -0.03 & -3.16 & -0.50 & -0.03 \\
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\ce{NH3} & 297.46 & -21.21 & -7.62 & -3.01 & -1.54 & -4.42 & -0.62 & 0.07 & -4.42 & -0.62 & 0.07 \\
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\ce{NO} & 151.73 & -13.87 & -7.26 & -3.25 & -1.66 & -2.20 & -1.10 & 0.08 & -2.20 & -1.10 & 0.08 \\
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\ce{Na2} & 16.44 & -0.71 & -0.14 & -0.06 & -0.03 & 0.20 & 0.15 & 0.08 & 0.20 & 0.15 & 0.08 \\
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\ce{NaCl} & 99.61 & -11.48 & -5.41 & -2.26 & -1.16 & -4.34 & -2.13 & -0.52 & -4.34 & -2.13 & -0.52 \\
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\ce{O2} & 119.64 & -9.86 & -5.34 & -2.40 & -1.23 & -3.08 & -1.72 & -0.30 & -3.08 & -1.72 & -0.30 \\
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\ce{OH} & 107.08 & -8.37 & -3.27 & -1.34 & -0.69 & -2.23 & -0.63 & -0.08 & -2.23 & -0.63 & -0.08 \\
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\ce{P2} & 115.68 & -18.05 & -9.34 & -4.00 & -2.05 & -3.96 & -1.89 & 0.26 & -3.96 & -1.89 & 0.26 \\
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\ce{PH2} & 153.91 & -11.50 & -4.32 & -1.51 & -0.77 & -2.56 & -0.82 & 0.16 & -2.56 & -0.82 & 0.16 \\
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\ce{PH3} & 241.49 & -15.43 & -5.80 & -2.03 & -1.04 & -3.12 & -1.03 & 0.20 & -3.12 & -1.03 & 0.20 \\
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\ce{S2} & 103.07 & -12.76 & -7.34 & -3.28 & -1.68 & -5.69 & -3.18 & -0.95 & -5.69 & -3.18 & -0.95 \\
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\ce{SO} & 125.12 & -10.77 & -6.14 & -2.94 & -1.51 & -3.33 & -2.10 & -0.59 & -3.33 & -2.10 & -0.59 \\
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\ce{SO2} & 258.09 & -22.35 & -13.90 & -6.75 & -3.46 & -5.16 & -4.67 & -1.32 & -5.16 & -4.67 & -1.32 \\
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\ce{Si2} & 75.74 & -10.01 & -4.47 & -1.82 & -0.93 & -4.19 & -1.49 & -0.17 & -4.19 & -1.49 & -0.17 \\
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\ce{Si2H6} & 535.58 & -27.32 & -10.13 & -3.46 & -1.77 & -5.59 & -1.86 & 0.30 & -5.59 & -1.86 & 0.30 \\
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\ce{SiH2 ^1A_1} & 153.66 & -8.72 & -2.98 & -0.98 & -0.50 & -3.51 & -1.46 & -0.34 & -3.51 & -1.46 & -0.34 \\
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\ce{SiH2 ^3B_1} & 133.17 & -6.68 & -2.40 & -0.73 & -0.37 & -3.02 & -1.57 & -0.49 & -3.02 & -1.57 & -0.49 \\
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\ce{SiH3} & 227.99 & -10.53 & -3.72 & -1.15 & -0.59 & -1.82 & -0.74 & 0.12 & -1.82 & -0.74 & 0.12 \\
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||||
\ce{SiH4} & 324.59 & -14.10 & -4.88 & -1.52 & -0.78 & -1.91 & -0.58 & 0.33 & -1.91 & -0.58 & 0.33 \\
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\ce{SiO} & 191.48 & -11.34 & -6.72 & -3.15 & -1.61 & -0.76 & -1.18 & 0.12 & -0.76 & -1.18 & 0.12 \\
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\end{tabular}
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\end{ruledtabular}
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\end{table}
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@ -271,4 +273,63 @@
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\bibliography{../G2_srDFT}
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\end{document}
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Loading…
Reference in New Issue
Block a user