SUPPLEMENTAL MATERIAL
EMPIRICAL CORRECTIONS IN THE G3X AND G3X(CCSD) THEORIES COMBINED WITH A COMPACT EFFECTIVE PSEUDOPOTENTIAL
Cleuton de Souza Silvaa,b and Rogério Custodioa
a. Instituto de Química, Universidade Estadual de Campinas, Barão Geraldo, 13083-970 Campinas – São Paulo, Brazil, P. O. Box 6154
b. Instituto de Ciências Exatas e Tecnologia, Universidade Federal do Amazonas, Campus de Itacoatiara, 69100-021 Itacoatiara – Amazonas, Brazil
Contents
Table S.1: Truncated G3Large basis set adapted to be used along with the CEP pseudopotential in the G3X-CEP, G3X(CCSD)-CEP, EnAt1 and EnAt2 calculations. 2
Table S.2: Truncated G3XLarge basis set adapted to be used along with the CEP pseudopotential in the G3X-CEP, G3X(CCSD)-CEP, EnAt1 and EnAt2 calculations. 20
Table S.3: Experimental and theoretical enthalpies of formation (kcal mol-1) for the G3/05 test set. G3X, G3X-CEP, G3X(CCSD)-CEP, EnAt1 and EnAt2 are the differences between the experimental data and the G3X, G3X-CEP, G3X(CCSD)-CEP, G3X-CEP+EnAt1 and G3X(CCSD)-CEP+EnAt2 calculations, respectively. 38
Table S.4: Experimental and calculated ionization energies (in kcal mol-1) for the G3/05 test set for compounds containing elements of the first and second period of the periodic table. G3X, G3X-CEP, G3X(CCSD)-CEP, EnAt1 and EnAt2 are the differences between the experimental data and the G3X, G3X-CEP, G3X(CCSD)-CEP, G3X-CEP+EnAt1 and G3X(CCSD)-CEP+EnAt2 calculations, respectively. 47
Table S.5: Experimental and calculated electron affinities (in kcal mol-1) for the G3/05 test set for compounds containing elements of the first and second period of the periodic table. G3X, G3X-CEP, G3X(CCSD)-CEP, EnAt1 and EnAt2 are the differences between the experimental data and the G3X, G3X-CEP, G3X(CCSD)-CEP, G3X-CEP+EnAt1 and G3X(CCSD)-CEP+EnAt2 calculations, respectively. 49
Table S.6: Experimental and calculated proton affinities (in kcal mol-1) for the G3/05 test set. G3X, G3X-CEP, G3X(CCSD)-CEP, EnAt1 and EnAt2 are the differences between the experimental data and the G3X, G3X-CEP, G3X(CCSD)-CEP, G3X-CEP+EnAt1 and G3X(CCSD)-CEP+EnAt2 calculations, respectively. 50
Table S.7: Experimental and calculated atomization energy (D0) for the G3/05 test set (data in kcal mol-1) for molecules containing non-transition third-row elements. G3X, G3X-CEP, G3X(CCSD)-CEP, EnAt1 and EnAt2 are the differences between the experimental data and the G3X, G3X-CEP, G3X(CCSD)-CEP, G3X-CEP+EnAt1 and G3X(CCSD)-CEP+EnAt2 calculations, respectively. 50
Table S.1: Truncated G3Large basis set adapted to be used along with the CEP pseudopotential in the G3X-CEP, G3X(CCSD)-CEP, EnAt1 and EnAt2 calculations.
-H 0
S 3 1.00
0.3386500000D+02 0.2549380000D-01
0.5094790000D+01 0.1903730000D+00
0.1158790000D+01 0.8521610000D+00
S 1 1.00
0.3258400000D+00 0.1000000000D+01
S 1 1.00
0.1027410000D+00 0.1000000000D+01
S 1 1.00
0.3600000000D-01 0.1000000000D+01
P 1 1.00
0.1500000000D+01 0.1000000000D+01
P 1 1.00
0.3750000000D+00 0.1000000000D+01
****
-He 0
S 3 1.00
0.9812430000D+02 0.2874520000D-01
0.1476890000D+02 0.2080610000D+00
0.3318830000D+01 0.8376350000D+00
S 1 1.00
0.8740470000D+00 0.1000000000D+01
S 1 1.00
0.2445640000D+00 0.1000000000D+01
S 1 1.00
0.8600000000D-01 0.1000000000D+01
P 1 1.00
0.1500000000D+01 0.1000000000D+01
P 1 1.00
0.3750000000D+00 0.1000000000D+01
****
-Li 0
SP 3 1.00
0.4868900000D+01 0.9332930000D-01 0.3276610000D-01
0.8569240000D+00 0.9430450000D+00 0.1597920000D+00
0.2432270000D+00 -0.2798270000D-02 0.8856670000D+00
SP 1 1.00
0.6350700000D-01 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.2436830000D-01 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.7400000000D-02 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.4000000000D+00 0.1000000000D+01
D 1 1.00
0.1000000000D+00 0.1000000000D+01
F 1 1.00
0.1500000000D+00 0.1000000000D+01
P 1 1.00
0.04000000000000D+02 0.1000000000D+01
D 1 1.00
0.07000000000000D+02 0.1000000000D+01
****
-Be 0
SP 3 1.00
0.8309380000D+01 0.1086210000D+00 0.3613440000D-01
0.1740750000D+01 0.9273010000D+00 0.2169580000D+00
0.4858160000D+00 -0.2971690000D-02 0.8418390000D+00
SP 1 1.00
0.1636130000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.5672850000D-01 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.2070000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.5100000000D+00 0.1000000000D+01
D 1 1.00
0.1275000000D+00 0.1000000000D+01
F 1 1.00
0.2600000000D+00 0.1000000000D+01
P 1 1.00
0.07000000000000D+02 0.1000000000D+01
D 1 1.00
0.09000000000000D+02 0.1000000000D+01
****
-B 0
SP 3 1.00
0.1324150000D+02 0.1174430000D+00 0.4181000000D-01
0.3001660000D+01 0.9180020000D+00 0.2365750000D+00
0.9128560000D+00 -0.2651050000D-02 0.8162140000D+00
SP 1 1.00
0.3154540000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.9885630000D-01 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.3150000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.8020000000D+00 0.1000000000D+01
D 1 1.00
0.2005000000D+00 0.1000000000D+01
F 1 1.00
0.5000000000D+00 0.1000000000D+01
P 1 1.00
0.11000000000000D+02 0.1000000000D+01
D 1 1.00
0.13000000000000D+02 0.1000000000D+01
****
-C 0
SP 3 0.9889
0.2096420000D+02 0.1146600000D+00 0.4024870000D-01
0.4803310000D+01 0.9199990000D+00 0.2375940000D+00
0.1459330000D+01 -0.3030680000D-02 0.8158540000D+00
SP 1 0.9889
0.4834560000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 0.9889
0.1455850000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 0.9889
0.4380000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.1252000000D+01 0.1000000000D+01
D 1 1.00
0.3130000000D+00 0.1000000000D+01
F 1 1.00
0.8000000000D+00 0.1000000000D+01
P 1 0.9889
0.16000000000000D+02 0.1000000000D+01
D 1 1.00
0.15000000000000D+02 0.1000000000D+01
****
-N 0
SP 3 0.9639
0.3063310000D+02 0.1119060000D+00 0.3831190000D-01
0.7026140000D+01 0.9216660000D+00 0.2374030000D+00
0.2112050000D+01 -0.2569190000D-02 0.8175920000D+00
SP 1 0.9639
0.6840090000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 0.9639
0.2008780000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 0.9639
0.6390000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.1826000000D+01 0.1000000000D+01
D 1 1.00
0.4565000000D+00 0.1000000000D+01
F 1 1.00
0.1000000000D+01 0.1000000000D+01
P 1 0.9639
0.22000000000000D+02 0.1000000000D+01
D 1 1.00
0.15000000000000D+02 0.1000000000D+01
****
-O 0
SP 3 0.9349
0.4211750000D+02 0.1138890000D+00 0.3651140000D-01
0.9628370000D+01 0.9208110000D+00 0.2371530000D+00
0.2853320000D+01 -0.3274470000D-02 0.8197020000D+00
SP 1 0.9349
0.9056610000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 0.9349
0.2556110000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 0.9349
0.8450000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.2584000000D+01 0.1000000000D+01
D 1 1.00
0.6460000000D+00 0.1000000000D+01
F 1 1.00
0.1400000000D+01 0.1000000000D+01
P 1 0.9349
0.2700000000D+02 0.1000000000D+01
D 1 1.00
0.1600000000D+02 0.1000000000D+01
****
-F 0
SP 3 0.9222
0.5544410000D+02 0.1145360000D+00 0.3546090000D-01
0.1263230000D+02 0.9205120000D+00 0.2374510000D+00
0.3717560000D+01 -0.3378040000D-02 0.8204580000D+00
SP 1 0.9222
0.1165450000D+01 0.1000000000D+01 0.1000000000D+01
SP 1 0.9222
0.3218920000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 0.9222
0.1076000000D+00 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.3500000000D+01 0.1000000000D+01
D 1 1.00
0.8750000000D+00 0.1000000000D+01
F 1 1.00
0.1850000000D+01 0.1000000000D+01
P 1 0.9222
0.3300000000D+02 0.1000000000D+01
D 1 1.00
0.1800000000D+02 0.1000000000D+01
****
-Ne 0
SP 3 1.00
0.6912110000D+02 0.1191490000D+00 0.3565740000D-01
0.1583500000D+02 0.9173750000D+00 0.2394770000D+00
0.4673260000D+01 -0.4058390000D-02 0.8184610000D+00
SP 1 1.00
0.1457560000D+01 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.3970570000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.1300000000D+00 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.4608000000D+01 0.1000000000D+01
D 1 1.00
0.1152000000D+01 0.1000000000D+01
F 1 1.00
0.2500000000D+01 0.1000000000D+01
P 1 1.00
0.4000000000D+02 0.1000000000D+01
D 1 1.00
0.2200000000D+02 0.1000000000D+01
****
-Na 0
S 3 1.00
0.3877730000D+02 0.3747620000D+00
0.1457590000D+02 0.5757690000D+00
0.5269930000D+01 0.1129330000D+00
S 1 1.00
0.1827770000D+01 0.1000000000D+01
S 1 1.00
0.6199480000D+00 0.1000000000D+01
S 1 1.00
0.5724000000D-01 0.1000000000D+01
S 1 1.00
0.2404800000D-01 0.1000000000D+01
P 4 1.00
0.1446450000D+03 0.1148500000D-01
0.3390740000D+02 0.8238300000D-01
0.1062850000D+02 0.3196580000D+00
0.3823890000D+01 0.7012950000D+00
P 2 1.00
0.1444290000D+01 0.6385060000D+00
0.5526210000D+00 0.4253650000D+00
P 1 1.00
0.1887200000D+00 0.1000000000D+01
P 1 1.00
0.4650100000D-01 0.1000000000D+01
P 1 1.00
0.1628500000D-01 0.1000000000D+01
SP 1 1.00
0.7600000000D-02 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.7000000000D+00 0.1000000000D+01
D 1 1.00
0.1750000000D+00 0.1000000000D+01
D 1 1.00
0.4375000000D-01 0.1000000000D+01
F 1 1.00
0.3000000000D+00 0.1000000000D+01
F 1 1.00
0.7500000000D-01 0.1000000000D+01
D 1 1.00
0.0400000000D+02 0.1000000000D+01
F 1 1.00
0.0400000000D+02 0.1000000000D+01
****
-Mg 0
S 3 1.00
0.5139830000D+02 0.2513550000D+00
0.1991960000D+02 0.6186710000D+00
0.8024740000D+01 0.1884170000D+00
S 1 1.00
0.2508170000D+01 0.1000000000D+01
S 1 1.00
0.8715310000D+00 0.1000000000D+01
S 1 1.00
0.1081880000D+00 0.1000000000D+01
S 1 1.00
0.4013000000D-01 0.1000000000D+01
P 4 1.00
0.1938540000D+03 0.1018800000D-01
0.4544200000D+02 0.7536000000D-01
0.1418640000D+02 0.3074190000D+00
0.5057510000D+01 0.7175750000D+00
P 2 1.00
0.1888610000D+01 0.6673390000D+00
0.7226520000D+00 0.3946490000D+00
P 1 1.00
0.2364170000D+00 0.1000000000D+01
P 1 1.00
0.9335800000D-01 0.1000000000D+01
P 1 1.00
0.3480900000D-01 0.1000000000D+01
SP 1 1.00
0.1460000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.7000000000D+00 0.1000000000D+01
D 1 1.00
0.1750000000D+00 0.1000000000D+01
D 1 1.00
0.4375000000D-01 0.1000000000D+01
F 1 1.00
0.4000000000D+00 0.1000000000D+01
F 1 1.00
0.1000000000D+00 0.1000000000D+01
D 1 1.00
0.0400000000D+02 0.1000000000D+01
F 1 1.00
0.0500000000D+02 0.1000000000D+01
****
-Al 0
S 3 1.00
0.6400550000D+02 0.2023050000D+00
0.2529250700D+02 0.6247900000D+00
0.1053491000D+02 0.2274390000D+00
S 1 1.00
0.3206711000D+01 0.1000000000D+01
S 1 1.00
0.1152555000D+01 0.1000000000D+01
S 1 1.00
0.1766780000D+00 0.1000000000D+01
S 1 1.00
0.6523700000D-01 0.1000000000D+01
P 4 1.00
0.2592836200D+03 0.9448000000D-02
0.6107687000D+02 0.7097400000D-01
0.1930323700D+02 0.2956360000D+00
0.7010882000D+01 0.7282190000D+00
P 2 1.00
0.2673865000D+01 0.6444670000D+00
0.1036596000D+01 0.4174130000D+00
P 1 1.00
0.3168190000D+00 0.1000000000D+01
P 1 1.00
0.1142570000D+00 0.1000000000D+01
P 1 1.00
0.4139700000D-01 0.1000000000D+01
SP 1 1.00
0.3180000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.1300000000D+01 0.1000000000D+01
D 1 1.00
0.3250000000D+00 0.1000000000D+01
D 1 1.00
0.8125000000D-01 0.1000000000D+01
F 1 1.00
0.5000000000D+00 0.1000000000D+01
F 1 1.00
0.1250000000D+00 0.1000000000D+01
D 1 1.00
0.0600000000D+02 0.1000000000D+01
F 1 1.00
0.0600000000D+02 0.1000000000D+01
****
-Si 0
S 3 1.00
0.7762916800D+02 0.1778810000D+00
0.3063080700D+02 0.6277650000D+00
0.1280129500D+02 0.2476230000D+00
S 1 1.00
0.3926866000D+01 0.1000000000D+01
S 1 1.00
0.1452343000D+01 0.1000000000D+01
S 1 1.00
0.2562340000D+00 0.1000000000D+01
S 1 1.00
0.9427900000D-01 0.1000000000D+01
P 4 1.00
0.3354831900D+03 0.8866000000D-02
0.7890036600D+02 0.6829900000D-01
0.2498815000D+02 0.2909580000D+00
0.9219711000D+01 0.7321170000D+00
P 2 1.00
0.3621140000D+01 0.6198790000D+00
0.1451310000D+01 0.4391480000D+00
P 1 1.00
0.5049770000D+00 0.1000000000D+01
P 1 1.00
0.1863170000D+00 0.1000000000D+01
P 1 1.00
0.6543200000D-01 0.1000000000D+01
SP 1 1.00
0.3310000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.1800000000D+01 0.1000000000D+01
D 1 1.00
0.4500000000D+00 0.1000000000D+01
D 1 1.00
0.1125000000D+00 0.1000000000D+01
F 1 1.00
0.6400000000D+00 0.1000000000D+01
F 1 1.00
0.1600000000D+00 0.1000000000D+01
D 1 1.00
0.0800000000D+02 0.1000000000D+01
F 1 1.00
0.0700000000D+02 0.1000000000D+01
****
-P
S 3 0.8146
91.156500 1.641617E-01
36.225700 6.259097E-01
15.211300 2.620744E-01
S 1 0.8146
4.713800 1.000000E+00
S 1 0.8146
1.782700 1.000000E+00
S 1 0.8146
0.342500 1.000000E+00
S 1 0.8146
0.124600 1.000000E+00
P 4 0.8146
384.840000 8.967875E-03
90.552000 6.904902E-02
28.806000 2.928770E-01
10.688000 7.292494E-01
P 2 0.8146
4.252100 6.325822E-01
1.740500 4.232996E-01
P 1 0.8146
0.597900 1.000000E+00
P 1 0.8146
0.229200 1.000000E+00
P 1 0.8146
0.083800 1.000000E+00
SP 1 0.8146
.3480000000D-01 .1000000000D+01 .1000000000D+01
D 1 1.00
.2200000000D+01 .1000000000D+01
D 1 1.00
.5500000000D+00 .1000000000D+01
D 1 1.00
.1375000000D+00 .1000000000D+01
F 1 1.00
.9000000000D+00 .1000000000D+01
F 1 1.00
.2250000000D+00 .1000000000D+01
D 1 1.00
0.1000000000D+02 0.1000000000D+01
F 1 1.00
0.0900000000D+02 0.1000000000D+01
****
-S 0
S 3 1.10158
108.702000 1.427905E-01
43.155300 6.246934E-01
18.107900 2.834835E-01
S 1 1.10158
5.570500 1.000000E+00
S 1 1.10158
2.142700 1.000000E+00
S 1 1.10158
0.434000 1.000000E+00
S 1 1.10158
0.157000 1.000000E+00
P 4 1.10158
495.040000 8.196253E-03
117.220000 6.364204E-02
37.507000 2.788060E-01
13.910000 7.447404E-01
P 2 1.10158
5.504500 6.168248E-01
2.243300 4.402946E-01
P 1 1.10158
0.776200 1.000000E+00
P 1 1.10158
0.291900 1.000000E+00
P 1 1.10158
0.102900 1.000000E+00
SP 1 1.10158
.4050000000D-01 .1000000000D+01 .1000000000D+01
D 1 1.00
.2600000000D+01 .1000000000D+01
D 1 1.00
.6500000000D+00 .1000000000D+01
D 1 1.00
.1625000000D+00 .1000000000D+01
F 1 1.00
.1100000000D+01 .1000000000D+01
F 1 1.00
.2750000000D+00 .1000000000D+01
D 1 1.00
0.1100000000D+02 0.1000000000D+01
F 1 1.00
0.1000000000D+02 0.1000000000D+01
****
-Cl 0
S 3 1.0548
124.538000 1.370443E-01
49.513500 6.231380E-01
20.805600 2.903279E-01
S 1 1.0548
6.464800 .100000D+01
S 1 1.0548
2.525400 .100000D+01
S 1 1.0548
0.537800 .100000D+01
S 1 1.0548
0.193500 .100000D+01
P 4 1.0548
589.780000 7.873332E-03
139.850000 6.155460E-02
44.795000 2.742514E-01
16.612000 7.498994E-01
P 2 1.0548
6.599500 6.147640E-01
2.714100 4.413416E-01
P 1 1.0548
0.952800 .100000D+01
P 1 1.0548
0.358000 .100000D+01
P 1 1.0548
0.125000 .100000D+01
SP 1 1.0548
.4830000000D-01 .1000000000D+01 .1000000000D+01
D 1 1.00
.3000000000D+01 .1000000000D+01
D 1 1.00
.7500000000D+00 .1000000000D+01
D 1 1.00
.1875000000D+00 .1000000000D+01
F 1 1.00
.1400000000D+01 .1000000000D+01
F 1 1.00
.3500000000D+00 .1000000000D+01
D 1 1.00
0.1300000000D+02 0.1000000000D+01
F 1 1.00
0.1200000000D+02 0.1000000000D+01
****
-Ar 0
S 3 1.00
138.160000 1.435931E-01
54.989100 6.231142E-01
23.170700 2.840810E-01
S 1 1.00
7.377860 1.000000E+00
S 1 1.00
2.923690 1.000000E+00
S 1 1.00
0.650405 1.000000E+00
S 1 1.00
0.232825 1.000000E+00
P 4 1.00
663.062000 7.820021E-03
157.093000 6.148333E-02
50.231100 2.754731E-01
18.635300 7.488402E-01
P 2 1.00
7.446540 -6.282210E-01
3.095700 -4.260202E-01
P 1 1.00
1.106460 1.000000E+00
P 1 1.00
0.415601 1.000000E+00
P 1 1.00
0.145449 1.000000E+00
SP 1 1.00
0.6000000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.3400000000D+01 0.1000000000D+01
D 1 1.00
0.8500000000D+00 0.1000000000D+01
D 1 1.00
0.2125000000D+00 0.1000000000D+01
F 1 1.00
0.1700000000D+01 0.1000000000D+01
F 1 1.00
0.4250000000D+00 0.1000000000D+01
D 1 1.00
0.1500000000D+02 0.1000000000D+01
F 1 1.00
0.1400000000D+02 0.1000000000D+01
****
-K 0
S 3 1.00
249.452200 8.810857E-02
69.999200 6.147206E-01
29.242930 3.532877E-01
S 1 1.00
8.392400 1.000000E+00
S 1 1.00
3.399001 1.000000E+00
S 1 1.00
0.834596 1.000000E+00
S 1 1.00
0.322037 1.000000E+00
S 1 1.00
0.094046 1.000000E+00
S 1 1.00
0.027464 1.000000E+00
P 6 1.00
4400.036000 4.154856E-04
1042.028000 3.643300E-03
340.015100 2.002363E-02
129.694200 8.321021E-02
53.476600 2.789242E-01
22.930090 7.059939E-01
P 2 1.00
9.931515 5.633295E-01
4.321735 4.874805E-01
P 1 1.00
1.790327 1.000000E+00
P 1 1.00
0.702128 1.000000E+00
P 1 1.00
0.260909 1.000000E+00
P 1 1.00
0.046794 1.000000E+00
P 1 1.00
0.016540 1.000000E+00
D 3 1.00
15.597880 5.981848E-02
4.148569 3.055979E-01
1.341566 7.724437E-01
D 1 1.00
.437806 1.000000E+00
D 1 1.00
.131287 1.000000E+00
SP 1 1.0
0.007 0.1000000000D+01 0.1000000000D+01
D 1 1.0
0.2 1.0
D 1 1.0
0.05 1.0
D 1 1.0
0.0125 1.0
F 1 1.0
2.4 1.0
F 1 1.0
0.6 1.0
D 1 1.0
15.0 1.0
F 1 1.0
17.0 1.0
****
-Ca 0
S 3 1.00
274.053900 8.883376E-02
77.728410 6.120359E-01
32.667310 3.548442E-01
S 1 1.00
9.491802 1.000000E+00
S 1 1.00
3.907649 1.000000E+00
S 1 1.00
1.047484 1.000000E+00
S 1 1.00
0.427538 1.000000E+00
S 1 1.00
0.137616 1.000000E+00
S 1 1.00
0.044296 1.000000E+00
P 6 1.00
4982.321000 4.239919E-04
1182.910000 3.709210E-03
385.140400 2.058408E-02
146.920500 8.518204E-02
61.277180 2.792454E-01
26.754290 7.018461E-01
P 2 1.00
11.798230 5.488426E-01
5.224737 5.001303E-01
P 1 1.00
2.237407 1.000000E+00
P 1 1.00
0.916006 1.000000E+00
P 1 1.00
0.360013 1.000000E+00
P 1 1.00
0.084774 1.000000E+00
P 1 1.00
0.030628 1.000000E+00
D 3 1.00
17.379120 5.981848E-02
4.622325 3.055979E-01
1.494769 7.724437E-01
D 1 1.00
.487802 1.000000E+00
D 1 1.00
.146280 1.000000E+00
SP 1 1.0
0.015 1.0 1.0
D 1 1.0
0.2 1.0
D 1 1.0
0.05 1.0
D 1 1.0
0.0125 1.0
F 1 1.0
2.4 1.0
F 1 1.0
0.6 1.0
D 1 1.0
16.0 1.0
F 1 1.0
19.0 1.0
****
-Ga 0
S 3 1.00
682.838500 8.747540E-02
195.225600 6.018123E-01
83.176310 3.655150E-01
S 1 1.00
25.277420 1.000000E+00
S 1 1.00
10.913140 1.000000E+00
S 1 1.00
3.378186 1.000000E+00
S 1 1.00
1.335003 1.000000E+00
S 1 1.00
0.192144 1.000000E+00
S 1 1.00
0.070438 1.000000E+00
P 4 1.00
4979.214000 4.910782E-03
1180.229000 4.206382E-02
381.918600 2.207828E-01
144.820000 8.044421E-01
P 3 1.00
60.463820 3.218199E-01
26.636360 4.780525E-01
11.896930 3.002092E-01
P 2 1.00
8.057676 3.057692E-01
3.970334 7.252840E-01
P 1 1.00
1.894128 1.000000E+00
P 1 1.00
0.824089 1.000000E+00
P 1 1.00
0.193293 1.000000E+00
P 1 1.00
0.055856 1.000000E+00
D 3 1.00
65.341550 5.575018E-02
18.498370 3.076190E-01
6.315129 7.634792E-01
D 1 1.00
2.163386 1.000000E+00
D 1 1.00
0.666699 1.000000E+00
SP 1 1.0
0.0138 1.0 1.0
D 1 1.0
1.2 1.0
D 1 1.0
0.3 1.0
D 1 1.0
0.075 1.0
F 1 1.0
0.8 1.0
F 1 1.0
0.2 1.0
D 1 1.0
49.0 1.0
F 1 1.0
5.0 1.0
****
-Ge 0
S 3 1.00
728.586400 8.742576E-02
208.504900 6.008180E-01
89.001060 3.664417E-01
S 1 1.00
27.144710 1.000000E+00
S 1 1.00
11.772660 1.000000E+00
S 1 1.00
3.733565 1.000000E+00
S 1 1.00
1.504531 1.000000E+00
S 1 1.00
0.243793 1.000000E+00
S 1 1.00
0.090974 1.000000E+00
P 4 1.00
5239.829000 4.886294E-03
1241.554000 4.187696E-02
401.400000 2.202140E-01
151.819700 8.052598E-01
P 3 1.00
63.114800 3.317036E-01
27.729400 4.808833E-01
12.313510 2.877933E-01
P 2 1.00
8.410451 3.103083E-01
3.871381 7.268281E-01
P 1 1.00
1.763903 1.000000E+00
P 1 1.00
0.746823 1.000000E+00
P 1 1.00
0.230359 1.000000E+00
P 1 1.00
0.073212 1.000000E+00
D 3 1.00
74.751330 5.332128E-02
21.298950 3.009604E-01
7.342004 7.684319E-01
D 1 1.00
2.564442 1.000000E+00
D 1 1.00
0.819459 1.000000E+00
SP 1 1.0
0.0317 1.0 1.0
D 1 1.0
1.2 1.0
D 1 1.0
0.3 1.0
D 1 1.0
0.075 1.0
F 1 1.0
0.8 1.0
F 1 1.0
0.2 1.0
D 1 1.0
53.0 1.0
F 1 1.0
6.0 1.0
****
-As 0
S 3 0.8673
772.309700 8.799553E-02
221.664200 6.004921E-01
94.805900 3.661217E-01
S 1 0.8673
29.100960 1.000000E+00
S 1 0.8673
12.675370 1.000000E+00
S 1 0.8673
4.110524 1.000000E+00
S 1 0.8673
1.686066 1.000000E+00
S 1 0.8673
0.297789 1.000000E+00
S 1 0.8673
0.112518 1.000000E+00
P 4 0.8673
5650.069000 4.858169E-03
1339.307000 4.164741E-02
433.157600 2.194459E-01
163.867900 8.060091E-01
P 3 0.8673
68.063360 3.301951E-01
29.804790 4.831738E-01
13.144230 2.877985E-01
P 2 0.8673
8.937471 3.127145E-01
4.018508 7.266892E-01
P 1 0.8673
1.786613 1.000000E+00
P 1 0.8673
0.686420 1.000000E+00
P 1 0.8673
0.253641 1.000000E+00
P 1 0.8673
0.087462 1.000000E+00
D 3 1.0
84.413030 5.138075E-02
24.178010 2.956335E-01
8.400142 7.723814E-01
D 1 1.00
2.979857 1.000000E+00
D 1 1.00
0.978767 1.000000E+00
SP 1 0.8673
0.0315 1.0 1.0
D 1 1.0
1.2 1.0
D 1 1.0
0.3 1.0
D 1 1.0
0.075 1.0
F 1 1.0
0.8 1.0
F 1 1.0
0.2 1.0
D 1 1.0
58.0 1.0
F 1 1.0
6.0 1.0
****
-Se 0
S 3 0.8411
821.647300 8.773439E-02
236.032300 5.993777E-01
101.104100 3.673669E-01
S 1 0.8411
31.078280 1.000000E+00
S 1 0.8411
13.591550 1.000000E+00
S 1 0.8411
4.500276 1.000000E+00
S 1 0.8411
1.875850 1.000000E+00
S 1 0.8411
0.357009 1.000000E+00
S 1 0.8411
0.135548 1.000000E+00
P 4 0.8411
5993.233000 4.864288E-03
1420.511000 4.170700E-02
459.677200 2.195884E-01
174.075900 8.057620E-01
P 3 0.8411
72.393590 3.316909E-01
31.767150 4.830542E-01
14.036690 2.859398E-01
P 2 0.8411
9.628360 3.116117E-01
4.316138 7.279810E-01
P 1 0.8411
1.918425 1.000000E+00
P 1 0.8411
0.707717 1.000000E+00
P 1 0.8411
0.272431 1.000000E+00
P 1 0.8411
0.095172 1.000000E+00
D 3 1.00
94.444350 4.975580E-02
27.171820 2.911433E-01
9.504132 7.756932E-01
D 1 1.00
3.416003 1.000000E+00
D 1 1.00
1.147657 1.000000E+00
SP 1 0.8411
0.0345 1.0 1.0
D 1 1.0
1.2 1.0
D 1 1.0
0.3 1.0
D 1 1.0
0.075 1.0
F 1 1.0
0.8 1.0
F 1 1.0
0.2 1.0
D 1 1.0
63.0 1.0
F 1 1.0
7.0 1.0
****
-Br 0
S 3 0.8572
865.750500 8.827931E-02
250.069300 5.986012E-01
107.386900 3.674312E-01
S 1 0.8572
33.160040 1.000000E+00
S 1 0.8572
14.560010 1.000000E+00
S 1 0.8572
4.911616 1.000000E+00
S 1 0.8572
2.076963 1.000000E+00
S 1 0.8572
0.419732 1.000000E+00
S 1 0.8572
0.160287 1.000000E+00
P 4 0.8572
6545.221000 4.743784E-03
1549.336000 4.088669E-02
500.091000 2.173950E-01
188.660000 8.084159E-01
P 3 0.8572
78.165830 3.292574E-01
34.226100 4.835649E-01
15.125040 2.880806E-01
P 2 0.8572
10.398860 3.100625E-01
4.700037 7.286757E-01
P 1 0.8572
2.116383 1.000000E+00
P 1 0.8572
0.792393 1.000000E+00
P 1 0.8572
0.308112 1.000000E+00
P 1 0.8572
0.108513 1.000000E+00
D 3 1.00
104.823100 4.837063E-02
30.269750 2.873196E-01
10.648190 7.785240E-01
D 1 1.00
3.869545 1.000000E+00
D 1 1.00
1.323971 1.000000E+00
SP 1 0.8572
0.0382 1.0 1.0
D 1 1.0
1.2 1.0
D 1 1.0
0.3 1.0
D 1 1.0
0.075 1.0
F 1 1.0
0.8 1.0
F 1 1.0
0.2 1.0
D 1 1.0
68.0 1.0
F 1 1.0
7.0 1.0
****
-Kr 0
S 3 1.00
925.387100 8.742331E-02
265.906000 5.977898E-01
114.190800 3.690922E-01
S 1 1.00
35.248140 1.000000E+00
S 1 1.00
15.532710 1.000000E+00
S 1 1.00
5.332949 1.000000E+00
S 1 1.00
2.284816 1.000000E+00
S 1 1.00
0.484218 1.000000E+00
S 1 1.00
0.185298 1.000000E+00
P 4 1.00
6880.168000 4.825233E-03
1630.817000 4.143591E-02
527.944000 2.188400E-01
200.186700 8.064212E-01
P 3 1.00
83.464630 3.266954E-01
36.756340 4.819409E-01
16.311580 2.914607E-01
P 2 1.00
11.244750 3.073792E-01
5.136835 7.302153E-01
P 1 1.00
2.346469 1.000000E+00
P 1 1.00
0.899456 1.000000E+00
P 1 1.00
0.352743 1.000000E+00
P 1 1.00
0.125235 1.000000E+00
D 3 1.00
115.525700 4.719217E-02
33.465880 2.840674E-01
11.831150 7.809177E-01
D 1 1.00
4.340416 1.000000E+00
D 1 1.00
1.507793 1.000000E+00
SP 1 1.0
0.0525 1.0 1.0
D 1 1.0
1.2 1.0
D 1 1.0
0.3 1.0
D 1 1.0
0.075 1.0
F 1 1.0
0.8 1.0
F 1 1.0
0.2 1.0
D 1 1.0
73.0 1.0
F 1 1.0
8.0 1.0
****
Table S.2: Truncated G3XLarge basis set adapted to be used along with the CEP pseudopotential in the G3X-CEP, G3X(CCSD)-CEP, EnAt1 and EnAt2 calculations.
-H 0
S 3 1.00
0.3386500000D+02 0.2549380000D-01
0.5094790000D+01 0.1903730000D+00
0.1158790000D+01 0.8521610000D+00
S 1 1.00
0.3258400000D+00 0.1000000000D+01
S 1 1.00
0.1027410000D+00 0.1000000000D+01
S 1 1.00
0.3600000000D-01 0.1000000000D+01
P 1 1.00
0.1500000000D+01 0.1000000000D+01
P 1 1.00
0.3750000000D+00 0.1000000000D+01
****
-He 0
S 3 1.00
0.9812430000D+02 0.2874520000D-01
0.1476890000D+02 0.2080610000D+00
0.3318830000D+01 0.8376350000D+00
S 1 1.00
0.8740470000D+00 0.1000000000D+01
S 1 1.00
0.2445640000D+00 0.1000000000D+01
S 1 1.00
0.8600000000D-01 0.1000000000D+01
P 1 1.00
0.1500000000D+01 0.1000000000D+01
P 1 1.00
0.3750000000D+00 0.1000000000D+01
****
-Li 0
SP 3 1.00
0.4868900000D+01 0.9332930000D-01 0.3276610000D-01
0.8569240000D+00 0.9430450000D+00 0.1597920000D+00
0.2432270000D+00 -0.2798270000D-02 0.8856670000D+00
SP 1 1.00
0.6350700000D-01 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.2436830000D-01 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.7400000000D-02 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.4000000000D+00 0.1000000000D+01
D 1 1.00
0.1000000000D+00 0.1000000000D+01
F 1 1.00
0.1500000000D+00 0.1000000000D+01
P 1 1.00
0.0400000000D+02 0.1000000000D+01
D 1 1.00
0.0700000000D+02 0.1000000000D+01
****
-Be 0
SP 3 1.00
0.8309380000D+01 0.1086210000D+00 0.3613440000D-01
0.1740750000D+01 0.9273010000D+00 0.2169580000D+00
0.4858160000D+00 -0.2971690000D-02 0.8418390000D+00
SP 1 1.00
0.1636130000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.5672850000D-01 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.2070000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.5100000000D+00 0.1000000000D+01
D 1 1.00
0.1275000000D+00 0.1000000000D+01
F 1 1.00
0.2600000000D+00 0.1000000000D+01
P 1 1.00
0.0700000000D+02 0.1000000000D+01
D 1 1.00
0.0900000000D+02 0.1000000000D+01
****
-B 0
SP 3 1.00
0.1324150000D+02 0.1174430000D+00 0.4181000000D-01
0.3001660000D+01 0.9180020000D+00 0.2365750000D+00
0.9128560000D+00 -0.2651050000D-02 0.8162140000D+00
SP 1 1.00
0.3154540000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.9885630000D-01 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.3150000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.8020000000D+00 0.1000000000D+01
D 1 1.00
0.2005000000D+00 0.1000000000D+01
F 1 1.00
0.5000000000D+00 0.1000000000D+01
P 1 1.00
0.1100000000D+02 0.1000000000D+01
D 1 1.00
0.1300000000D+02 0.1000000000D+01
****
-C 0
SP 3 0.9889
0.2096420000D+02 0.1146600000D+00 0.4024870000D-01
0.4803310000D+01 0.9199990000D+00 0.2375940000D+00
0.1459330000D+01 -0.3030680000D-02 0.8158540000D+00
SP 1 0.9889
0.4834560000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 0.9889
0.1455850000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 0.9889
0.4380000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.1252000000D+01 0.1000000000D+01
D 1 1.00
0.3130000000D+00 0.1000000000D+01
F 1 1.00
0.8000000000D+00 0.1000000000D+01
P 1 0.9889
0.1600000000D+02 0.1000000000D+01
D 1 1.00
0.1500000000D+02 0.1000000000D+01
****
-N 0
SP 3 0.9639
0.3063310000D+02 0.1119060000D+00 0.3831190000D-01
0.7026140000D+01 0.9216660000D+00 0.2374030000D+00
0.2112050000D+01 -0.2569190000D-02 0.8175920000D+00
SP 1 0.9639
0.6840090000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 0.9639
0.2008780000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 0.9639
0.6390000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.1826000000D+01 0.1000000000D+01
D 1 1.00
0.4565000000D+00 0.1000000000D+01
F 1 1.00
0.1000000000D+01 0.1000000000D+01
P 1 0.9639
0.2200000000D+02 0.1000000000D+01
D 1 1.00
0.1500000000D+02 0.1000000000D+01
****
-O 0
SP 3 0.9349
0.4211750000D+02 0.1138890000D+00 0.3651140000D-01
0.9628370000D+01 0.9208110000D+00 0.2371530000D+00
0.2853320000D+01 -0.3274470000D-02 0.8197020000D+00
SP 1 0.9349
0.9056610000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 0.9349
0.2556110000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 0.9349
0.8450000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.2584000000D+01 0.1000000000D+01
D 1 1.00
0.6460000000D+00 0.1000000000D+01
F 1 1.00
0.1400000000D+01 0.1000000000D+01
P 1 0.9349
0.2700000000D+02 0.1000000000D+01
D 1 1.00
0.1600000000D+02 0.1000000000D+01
****
-F 0
SP 3 0.9222
0.5544410000D+02 0.1145360000D+00 0.3546090000D-01
0.1263230000D+02 0.9205120000D+00 0.2374510000D+00
0.3717560000D+01 -0.3378040000D-02 0.8204580000D+00
SP 1 0.9222
0.1165450000D+01 0.1000000000D+01 0.1000000000D+01
SP 1 0.9222
0.3218920000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 0.9222
0.1076000000D+00 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.3500000000D+01 0.1000000000D+01
D 1 1.00
0.8750000000D+00 0.1000000000D+01
F 1 1.00
0.1850000000D+01 0.1000000000D+01
P 1 0.9222
0.3300000000D+02 0.1000000000D+01
D 1 1.00
0.1800000000D+02 0.1000000000D+01
****
-Ne 0
SP 3 1.00
0.6912110000D+02 0.1191490000D+00 0.3565740000D-01
0.1583500000D+02 0.9173750000D+00 0.2394770000D+00
0.4673260000D+01 -0.4058390000D-02 0.8184610000D+00
SP 1 1.00
0.1457560000D+01 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.3970570000D+00 0.1000000000D+01 0.1000000000D+01
SP 1 1.00
0.1300000000D+00 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.4608000000D+01 0.1000000000D+01
D 1 1.00
0.1152000000D+01 0.1000000000D+01
F 1 1.00
0.2500000000D+01 0.1000000000D+01
P 1 1.00
0.4000000000D+02 0.1000000000D+01
D 1 1.00
0.2200000000D+02 0.1000000000D+01
****
-Na 0
S 3 1.00
0.3877730000D+02 0.3747620000D+00
0.1457590000D+02 0.5757690000D+00
0.5269930000D+01 0.1129330000D+00
S 1 1.00
0.1827770000D+01 0.1000000000D+01
S 1 1.00
0.6199480000D+00 0.1000000000D+01
S 1 1.00
0.5724000000D-01 0.1000000000D+01
S 1 1.00
0.2404800000D-01 0.1000000000D+01
P 4 1.00
0.1446450000D+03 0.1148500000D-01
0.3390740000D+02 0.8238300000D-01
0.1062850000D+02 0.3196580000D+00
0.3823890000D+01 0.7012950000D+00
P 2 1.00
0.1444290000D+01 0.6385060000D+00
0.5526210000D+00 0.4253650000D+00
P 1 1.00
0.1887200000D+00 0.1000000000D+01
P 1 1.00
0.4650100000D-01 0.1000000000D+01
P 1 1.00
0.1628500000D-01 0.1000000000D+01
SP 1 1.00
0.7600000000D-02 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.7000000000D+00 0.1000000000D+01
D 1 1.00
0.1750000000D+00 0.1000000000D+01
D 1 1.00
0.4375000000D-01 0.1000000000D+01
F 1 1.00
0.3000000000D+00 0.1000000000D+01
F 1 1.00
0.7500000000D-01 0.1000000000D+01
D 1 1.00
0.0400000000D+02 0.1000000000D+01
F 1 1.00
0.0400000000D+02 0.1000000000D+01
****
-Mg 0
S 3 1.00
0.5139830000D+02 0.2513550000D+00
0.1991960000D+02 0.6186710000D+00
0.8024740000D+01 0.1884170000D+00
S 1 1.00
0.2508170000D+01 0.1000000000D+01
S 1 1.00
0.8715310000D+00 0.1000000000D+01
S 1 1.00
0.1081880000D+00 0.1000000000D+01
S 1 1.00
0.4013000000D-01 0.1000000000D+01
P 4 1.00
0.1938540000D+03 0.1018800000D-01
0.4544200000D+02 0.7536000000D-01
0.1418640000D+02 0.3074190000D+00
0.5057510000D+01 0.7175750000D+00
P 2 1.00
0.1888610000D+01 0.6673390000D+00
0.7226520000D+00 0.3946490000D+00
P 1 1.00
0.2364170000D+00 0.1000000000D+01
P 1 1.00
0.9335800000D-01 0.1000000000D+01
P 1 1.00
0.3480900000D-01 0.1000000000D+01
SP 1 1.00
0.1460000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.7000000000D+00 0.1000000000D+01
D 1 1.00
0.1750000000D+00 0.1000000000D+01
D 1 1.00
0.4375000000D-01 0.1000000000D+01
F 1 1.00
0.4000000000D+00 0.1000000000D+01
F 1 1.00
0.1000000000D+00 0.1000000000D+01
D 1 1.00
0.0400000000D+02 0.1000000000D+01
F 1 1.00
0.0500000000D+02 0.1000000000D+01
****
-Al 0
S 3 1.00
0.6400550000D+02 0.2023050000D+00
0.2529250700D+02 0.6247900000D+00
0.1053491000D+02 0.2274390000D+00
S 1 1.00
0.3206711000D+01 0.1000000000D+01
S 1 1.00
0.1152555000D+01 0.1000000000D+01
S 1 1.00
0.1766780000D+00 0.1000000000D+01
S 1 1.00
0.6523700000D-01 0.1000000000D+01
P 4 1.00
0.2592836200D+03 0.9448000000D-02
0.6107687000D+02 0.7097400000D-01
0.1930323700D+02 0.2956360000D+00
0.7010882000D+01 0.7282190000D+00
P 2 1.00
0.2673865000D+01 0.6444670000D+00
0.1036596000D+01 0.4174130000D+00
P 1 1.00
0.3168190000D+00 0.1000000000D+01
P 1 1.00
0.1142570000D+00 0.1000000000D+01
P 1 1.00
0.4139700000D-01 0.1000000000D+01
SP 1 1.00
0.3180000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.1300000000D+01 0.1000000000D+01
D 1 1.00
0.3250000000D+00 0.1000000000D+01
D 1 1.00
0.8125000000D-01 0.1000000000D+01
F 1 1.00
0.5000000000D+00 0.1000000000D+01
F 1 1.00
0.1250000000D+00 0.1000000000D+01
D 1 1.00
0.0600000000D+02 0.1000000000D+01
F 1 1.00
0.0600000000D+02 0.1000000000D+01
G 1 1.00
0.3570000000D+00 0.1000000000D+01
****
-Si 0
S 3 1.00
0.7762916800D+02 0.1778810000D+00
0.3063080700D+02 0.6277650000D+00
0.1280129500D+02 0.2476230000D+00
S 1 1.00
0.3926866000D+01 0.1000000000D+01
S 1 1.00
0.1452343000D+01 0.1000000000D+01
S 1 1.00
0.2562340000D+00 0.1000000000D+01
S 1 1.00
0.9427900000D-01 0.1000000000D+01
P 4 1.00
0.3354831900D+03 0.8866000000D-02
0.7890036600D+02 0.6829900000D-01
0.2498815000D+02 0.2909580000D+00
0.9219711000D+01 0.7321170000D+00
P 2 1.00
0.3621140000D+01 0.6198790000D+00
0.1451310000D+01 0.4391480000D+00
P 1 1.00
0.5049770000D+00 0.1000000000D+01
P 1 1.00
0.1863170000D+00 0.1000000000D+01
P 1 1.00
0.6543200000D-01 0.1000000000D+01
SP 1 1.00
0.3310000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.1800000000D+01 0.1000000000D+01
D 1 1.00
0.4500000000D+00 0.1000000000D+01
D 1 1.00
0.1125000000D+00 0.1000000000D+01
F 1 1.00
0.6400000000D+00 0.1000000000D+01
F 1 1.00
0.1600000000D+00 0.1000000000D+01
D 1 1.00
0.0800000000D+02 0.1000000000D+01
F 1 1.00
0.0700000000D+02 0.1000000000D+01
G 1 1.00
0.4610000000D+00 0.1000000000D+01
****
-P 0
S 3 0.8146
91.156500 1.641617E-01
36.225700 6.259097E-01
15.211300 2.620744E-01
S 1 0.8146
4.713800 1.000000E+00
S 1 0.8146
1.782700 1.000000E+00
S 1 0.8146
0.342500 1.000000E+00
S 1 0.8146
0.124600 1.000000E+00
P 4 0.8146
384.840000 8.967875E-03
90.552000 6.904902E-02
28.806000 2.928770E-01
10.688000 7.292494E-01
P 2 0.8146
4.252100 6.325822E-01
1.740500 4.232996E-01
P 1 0.8146
0.597900 1.000000E+00
P 1 0.8146
0.229200 1.000000E+00
P 1 0.8146
0.083800 1.000000E+00
SP 1 0.8146
0.3480000000D-01 .1000000000D+01 .1000000000D+01
D 1 1.00
0.2200000000D+01 .1000000000D+01
D 1 1.00
0.5500000000D+00 .1000000000D+01
D 1 1.00
0.1375000000D+00 .1000000000D+01
F 1 1.00
0.9000000000D+00 .1000000000D+01
F 1 1.00
0.2250000000D+00 .1000000000D+01
D 1 1.00
0.10000000000D+02 0.1000000000D+01
F 1 1.00
0.09000000000D+02 0.1000000000D+01
G 1 1.00
0.59700000000D+00 0.1000000000D+01
****
-S 0
S 3 1.10158
108.702000 1.427905E-01
43.155300 6.246934E-01
18.107900 2.834835E-01
S 1 1.10158
5.570500 1.000000E+00
S 1 1.10158
2.142700 1.000000E+00
S 1 1.10158
0.434000 1.000000E+00
S 1 1.10158
0.157000 1.000000E+00
P 4 1.10158
495.040000 8.196253E-03
117.220000 6.364204E-02
37.507000 2.788060E-01
13.910000 7.447404E-01
P 2 1.10158
5.504500 6.168248E-01
2.243300 4.402946E-01
P 1 1.10158
0.776200 1.000000E+00
P 1 1.10158
0.291900 1.000000E+00
P 1 1.10158
0.102900 1.000000E+00
SP 1 1.10158
0.4050000000D-01 0.1000000000D+01 .1000000000D+01
D 1 1.00
0.2600000000D+01 0.1000000000D+01
D 1 1.00
0.6500000000D+00 0.1000000000D+01
D 1 1.00
0.1625000000D+00 0.1000000000D+01
F 1 1.00
0.1100000000D+01 0.1000000000D+01
F 1 1.00
0.2750000000D+00 0.1000000000D+01
D 1 1.00
0.1100000000D+02 0.1000000000D+01
F 1 1.00
0.1000000000D+02 0.1000000000D+01
G 1 1.00
0.6830000000D+00 0.1000000000D+01
****
-Cl
S 3 1.0548
124.538000 1.370443E-01
49.513500 6.231380E-01
20.805600 2.903279E-01
S 1 1.0548
6.464800 .100000D+01
S 1 1.0548
2.525400 .100000D+01
S 1 1.0548
0.537800 .100000D+01
S 1 1.0548
0.193500 .100000D+01
P 4 1.0548
589.780000 7.873332E-03
139.850000 6.155460E-02
44.795000 2.742514E-01
16.612000 7.498994E-01
P 2 1.0548
6.599500 6.147640E-01
2.714100 4.413416E-01
P 1 1.0548
0.952800 0.100000D+01
P 1 1.0548
0.358000 0.100000D+01
P 1 1.0548
0.125000 0.100000D+01
SP 1 1.0548
0.4830000000D-01 0.1000000000D+01 .1000000000D+01
D 1 1.00
0.3000000000D+01 0.1000000000D+01
D 1 1.00
0.7500000000D+00 0.1000000000D+01
D 1 1.00
0.1875000000D+00 0.1000000000D+01
F 1 1.00
0.1400000000D+01 0.1000000000D+01
F 1 1.00
0.3500000000D+00 0.1000000000D+01
D 1 1.00
0.1300000000D+02 0.1000000000D+01
F 1 1.00
0.1200000000D+02 0.1000000000D+01
G 1 1.00
0.8270000000D+00 0.1000000000D+01
****
-Ar
S 3 1.00
138.160000 1.435931E-01
54.989100 6.231142E-01
23.170700 2.840810E-01
S 1 1.00
7.377860 1.000000E+00
S 1 1.00
2.923690 1.000000E+00
S 1 1.00
0.650405 1.000000E+00
S 1 1.00
0.232825 1.000000E+00
P 4 1.00
663.062000 7.820021E-03
157.093000 6.148333E-02
50.231100 2.754731E-01
18.635300 7.488402E-01
P 2 1.00
7.446540 -6.282210E-01
3.095700 -4.260202E-01
P 1 1.00
1.106460 1.000000E+00
P 1 1.00
0.415601 1.000000E+00
P 1 1.00
0.145449 1.000000E+00
SP 1 1.00
0.6000000000D-01 0.1000000000D+01 0.1000000000D+01
D 1 1.00
0.3400000000D+01 0.1000000000D+01
D 1 1.00
0.8500000000D+00 0.1000000000D+01
D 1 1.00
0.2125000000D+00 0.1000000000D+01
F 1 1.00
0.1700000000D+01 0.1000000000D+01
F 1 1.00
0.4250000000D+00 0.1000000000D+01
D 1 1.00
0.1500000000D+02 0.1000000000D+01
F 1 1.00
0.1400000000D+02 0.1000000000D+01
G 1 1.00
0.1007000000D+01 0.1000000000D+01
****
-K 0
S 3 1.00
249.452200 8.810857E-02
69.999200 6.147206E-01
29.242930 3.532877E-01
S 1 1.00
8.392400 1.000000E+00
S 1 1.00
3.399001 1.000000E+00
S 1 1.00
0.834596 1.000000E+00
S 1 1.00
0.322037 1.000000E+00
S 1 1.00
0.094046 1.000000E+00
S 1 1.00
0.027464 1.000000E+00
P 6 1.00
4400.036000 4.154856E-04
1042.028000 3.643300E-03
340.015100 2.002363E-02
129.694200 8.321021E-02
53.476600 2.789242E-01
22.930090 7.059939E-01
P 2 1.00
9.931515 5.633295E-01
4.321735 4.874805E-01
P 1 1.00
1.790327 1.000000E+00
P 1 1.00
0.702128 1.000000E+00
P 1 1.00
0.260909 1.000000E+00
P 1 1.00
0.046794 1.000000E+00
P 1 1.00
0.016540 1.000000E+00
D 3 1.00
15.597880 5.981848E-02
4.148569 3.055979E-01
1.341566 7.724437E-01
D 1 1.00
.437806 1.000000E+00
D 1 1.00
.131287 1.000000E+00
SP 1 1.0
0.007 1.0 1.0
D 1 1.0
0.2 1.0
D 1 1.0
0.05 1.0
D 1 1.0
0.0125 1.0
F 1 1.0
2.4 1.0
F 1 1.0
0.6 1.0
D 1 1.0
15.0 1.0
F 1 1.0
17.0 1.0
****
-Ca 0
S 3 1.00
274.053900 8.883376E-02
77.728410 6.120359E-01
32.667310 3.548442E-01
S 1 1.00
9.491802 1.000000E+00
S 1 1.00
3.907649 1.000000E+00
S 1 1.00
1.047484 1.000000E+00
S 1 1.00
0.427538 1.000000E+00
S 1 1.00
0.137616 1.000000E+00
S 1 1.00
0.044296 1.000000E+00
P 6 1.00
4982.321000 4.239919E-04
1182.910000 3.709210E-03
385.140400 2.058408E-02
146.920500 8.518204E-02
61.277180 2.792454E-01
26.754290 7.018461E-01
P 2 1.00
11.798230 5.488426E-01
5.224737 5.001303E-01
P 1 1.00
2.237407 1.000000E+00
P 1 1.00
0.916006 1.000000E+00
P 1 1.00
0.360013 1.000000E+00
P 1 1.00
0.084774 1.000000E+00
P 1 1.00
0.030628 1.000000E+00
D 3 1.00
17.379120 5.981848E-02
4.622325 3.055979E-01
1.494769 7.724437E-01
D 1 1.00
.487802 1.000000E+00
D 1 1.00
.146280 1.000000E+00
SP 1 1.0
0.015 1.0 1.0
D 1 1.0
0.2 1.0
D 1 1.0
0.05 1.0
D 1 1.0
0.0125 1.0
F 1 1.0
2.4 1.0
F 1 1.0
0.6 1.0
D 1 1.0
16.0 1.0
F 1 1.0
19.0 1.0
****
-Ga 0
S 3 1.00
682.838500 8.747540E-02
195.225600 6.018123E-01
83.176310 3.655150E-01
S 1 1.00
25.277420 1.000000E+00
S 1 1.00
10.913140 1.000000E+00
S 1 1.00
3.378186 1.000000E+00
S 1 1.00
1.335003 1.000000E+00
S 1 1.00
0.192144 1.000000E+00
S 1 1.00
0.070438 1.000000E+00
P 4 1.00
4979.214000 4.910782E-03
1180.229000 4.206382E-02
381.918600 2.207828E-01
144.820000 8.044421E-01
P 3 1.00
60.463820 3.218199E-01
26.636360 4.780525E-01
11.896930 3.002092E-01
P 2 1.00
8.057676 3.057692E-01
3.970334 7.252840E-01
P 1 1.00
1.894128 1.000000E+00
P 1 1.00
0.824089 1.000000E+00
P 1 1.00
0.193293 1.000000E+00
P 1 1.00
0.055856 1.000000E+00
D 3 1.00
65.341550 5.575018E-02
18.498370 3.076190E-01
6.315129 7.634792E-01
D 1 1.00
2.163386 1.000000E+00
D 1 1.00
0.666699 1.000000E+00
SP 1 1.0
0.0138 1.0 1.0
D 1 1.0
1.2 1.0
D 1 1.0
0.3 1.0
D 1 1.0
0.075 1.0
F 1 1.0
0.8 1.0
F 1 1.0
0.2 1.0
D 1 1.0
49.0 1.0
F 1 1.0
5.0 1.0
G 1 1.0
0.403 1.0
****
-Ge 0
S 3 1.00
728.586400 8.742576E-02
208.504900 6.008180E-01
89.001060 3.664417E-01
S 1 1.00
27.144710 1.000000E+00
S 1 1.00
11.772660 1.000000E+00
S 1 1.00
3.733565 1.000000E+00
S 1 1.00
1.504531 1.000000E+00
S 1 1.00
0.243793 1.000000E+00
S 1 1.00
0.090974 1.000000E+00
P 4 1.00
5239.829000 4.886294E-03
1241.554000 4.187696E-02
401.400000 2.202140E-01
151.819700 8.052598E-01
P 3 1.00
63.114800 3.317036E-01
27.729400 4.808833E-01
12.313510 2.877933E-01
P 2 1.00
8.410451 3.103083E-01
3.871381 7.268281E-01
P 1 1.00
1.763903 1.000000E+00
P 1 1.00
0.746823 1.000000E+00
P 1 1.00
0.230359 1.000000E+00
P 1 1.00
0.073212 1.000000E+00
D 3 1.00
74.751330 5.332128E-02
21.298950 3.009604E-01
7.342004 7.684319E-01
D 1 1.00
2.564442 1.000000E+00
D 1 1.00
0.819459 1.000000E+00
SP 1 1.0
0.0317 1.0 1.0
D 1 1.0
1.2 1.0
D 1 1.0
0.3 1.0
D 1 1.0
0.075 1.0
F 1 1.0
0.8 1.0
F 1 1.0
0.2 1.0
D 1 1.0
53.0 1.0
F 1 1.0
6.0 1.0
G 1 1.0
0.468 1.0
****
-As 0
S 3 0.8673
772.309700 8.799553E-02
221.664200 6.004921E-01
94.805900 3.661217E-01
S 1 0.8673
29.100960 1.000000E+00
S 1 0.8673
12.675370 1.000000E+00
S 1 0.8673
4.110524 1.000000E+00
S 1 0.8673
1.686066 1.000000E+00
S 1 0.8673
0.297789 1.000000E+00
S 1 0.8673
0.112518 1.000000E+00
P 4 0.8673
5650.069000 4.858169E-03
1339.307000 4.164741E-02
433.157600 2.194459E-01
163.867900 8.060091E-01
P 3 0.8673
68.063360 3.301951E-01
29.804790 4.831738E-01
13.144230 2.877985E-01
P 2 0.8673
8.937471 3.127145E-01
4.018508 7.266892E-01
P 1 0.8673
1.786613 1.000000E+00
P 1 0.8673
0.686420 1.000000E+00
P 1 0.8673
0.253641 1.000000E+00
P 1 0.8673
0.087462 1.000000E+00
D 3 1.0
84.413030 5.138075E-02
24.178010 2.956335E-01
8.400142 7.723814E-01
D 1 1.00
2.979857 1.000000E+00
D 1 1.00
0.978767 1.000000E+00
SP 1 0.8673
0.0315 1.0 1.0
D 1 1.0
1.2 1.0
D 1 1.0
0.3 1.0
D 1 1.0
0.075 1.0
F 1 1.0
0.8 1.0
F 1 1.0
0.2 1.0
D 1 1.0
58.0 1.0
F 1 1.0
6.0 1.0
G 1 1.0
0.546 1.0
****
-Se 0
S 3 0.8411
821.647300 8.773439E-02
236.032300 5.993777E-01
101.104100 3.673669E-01
S 1 0.8411
31.078280 1.000000E+00
S 1 0.8411
13.591550 1.000000E+00
S 1 0.8411
4.500276 1.000000E+00
S 1 0.8411
1.875850 1.000000E+00
S 1 0.8411
0.357009 1.000000E+00
S 1 0.8411
0.135548 1.000000E+00
P 4 0.8411
5993.233000 4.864288E-03
1420.511000 4.170700E-02
459.677200 2.195884E-01
174.075900 8.057620E-01
P 3 0.8411
72.393590 3.316909E-01
31.767150 4.830542E-01
14.036690 2.859398E-01
P 2 0.8411
9.628360 3.116117E-01
4.316138 7.279810E-01
P 1 0.8411
1.918425 1.000000E+00
P 1 0.8411
0.707717 1.000000E+00
P 1 0.8411
0.272431 1.000000E+00
P 1 0.8411
0.095172 1.000000E+00
D 3 1.00
94.444350 4.975580E-02
27.171820 2.911433E-01
9.504132 7.756932E-01
D 1 1.00
3.416003 1.000000E+00
D 1 1.00
1.147657 1.000000E+00
SP 1 0.8411
0.0345 1.0 1.0
D 1 1.0
1.2 1.0
D 1 1.0
0.3 1.0
D 1 1.0
0.075 1.0
F 1 1.0
0.8 1.0
F 1 1.0
0.2 1.0
D 1 1.0
63.0 1.0
F 1 1.0
7.0 1.0
G 1 1.0
0.573 1.0
****
-Br 0
S 3 0.8572
865.750500 8.827931E-02
250.069300 5.986012E-01
107.386900 3.674312E-01
S 1 0.8572
33.160040 1.000000E+00
S 1 0.8572
14.560010 1.000000E+00
S 1 0.8572
4.911616 1.000000E+00
S 1 0.8572
2.076963 1.000000E+00
S 1 0.8572
0.419732 1.000000E+00
S 1 0.8572
0.160287 1.000000E+00
P 4 0.8572
6545.221000 4.743784E-03
1549.336000 4.088669E-02
500.091000 2.173950E-01
188.660000 8.084159E-01
P 3 0.8572
78.165830 3.292574E-01
34.226100 4.835649E-01
15.125040 2.880806E-01
P 2 0.8572
10.398860 3.100625E-01
4.700037 7.286757E-01
P 1 0.8572
2.116383 1.000000E+00
P 1 0.8572
0.792393 1.000000E+00
P 1 0.8572
0.308112 1.000000E+00
P 1 0.8572
0.108513 1.000000E+00
D 3 1.00
104.823100 4.837063E-02
30.269750 2.873196E-01
10.648190 7.785240E-01
D 1 1.00
3.869545 1.000000E+00
D 1 1.00
1.323971 1.000000E+00
SP 1 0.8572
0.0382 1.0 1.0
D 1 1.0
1.2 1.0
D 1 1.0
0.3 1.0
D 1 1.0
0.075 1.0
F 1 1.0
0.8 1.0
F 1 1.0
0.2 1.0
D 1 1.0
68.0 1.0
F 1 1.0
7.0 1.0
G 1 1.0
0.649 1.0
****
-Kr 0
S 3 1.00
925.387100 8.742331E-02
265.906000 5.977898E-01
114.190800 3.690922E-01
S 1 1.00
35.248140 1.000000E+00
S 1 1.00
15.532710 1.000000E+00
S 1 1.00
5.332949 1.000000E+00
S 1 1.00
2.284816 1.000000E+00
S 1 1.00
0.484218 1.000000E+00
S 1 1.00
0.185298 1.000000E+00
P 4 1.00
6880.168000 4.825233E-03
1630.817000 4.143591E-02
527.944000 2.188400E-01
200.186700 8.064212E-01
P 3 1.00
83.464630 3.266954E-01
36.756340 4.819409E-01
16.311580 2.914607E-01
P 2 1.00
11.244750 3.073792E-01
5.136835 7.302153E-01
P 1 1.00
2.346469 1.000000E+00
P 1 1.00
0.899456 1.000000E+00
P 1 1.00
0.352743 1.000000E+00
P 1 1.00
0.125235 1.000000E+00
D 3 1.00
115.525700 4.719217E-02
33.465880 2.840674E-01
11.831150 7.809177E-01
D 1 1.00
4.340416 1.000000E+00
D 1 1.00
1.507793 1.000000E+00
SP 1 1.0
0.0525 1.0 1.0
D 1 1.0
1.2 1.0
D 1 1.0
0.3 1.0
D 1 1.0
0.075 1.0
F 1 1.0
0.8 1.0
F 1 1.0
0.2 1.0
D 1 1.0
73.0 1.0
F 1 1.0
8.0 1.0
G 1 1.0
0.739 1.0
****
Table S.3: Experimental and theoretical enthalpies of formation (kcal mol-1) for the G3/05 test set. G3X, G3X-CEP, G3X(CCSD)-CEP, EnAt1 and EnAt2 are the differences between the experimental data and the G3X, G3X-CEP, G3X(CCSD)-CEP, G3X-CEP+EnAt1 and G3X(CCSD)-CEP+EnAt2 calculations, respectively.
Molecule / Exp(a) / ΔG3X / ΔG3X-CEP / ΔG3X(CCSD)-CEP / ΔEnAt1(b) / ΔEnAt2(c)SiF4 / -386.0 / 2.3 / 1.6 / 2.5 / 0.9 / 1.8
PF5 / -381.1 / -1.8 / 4.7 / 5.0 / 4.5 / 4.5
C2F6 / -321.3 / 3.1 / 0.7 / 0.8 / 0.7 / 0.6
Al2Cl6 / -309.7 / 7.8 / 6.7 / 7.6 / 0.0 / 0.0
SF6 / -291.7 / -0.5 / 2.6 / 3.0 / 2.2 / 2.4
AlF3 / -289.0 / 1.1 / 4.9 / 5.1 / 0.2 / 0.5
BF3 / -271,4 / -0,5 / -2,0 / -1,8 / 0,0 / -0,7
PF3 / -229.1 / -1.9 / -0.2 / -0.1 / -0.5 / -0.5
C6F6 / -228.4 / 3.1 / 0.6 / 0.6 / 0.2 / 0.3
CF4 / -223.0 / 0.9 / -0.4 / -0.2 / -0.3 / -0.3
C6F5Cl / -194.1 / 2.0 / -0.2 / -0.1 / -0.1 / -0.1
BeF2 / -190.3 / -3.5 / -0.2 / -0.1 / -0.8 / -0.7
CF3Cl / -169.5 / 0.1 / 0.1 / 0.3 / 0.6 / 0.4
CHF3 / -166.6 / 0.5 / -0.5 / -0.4 / -0.4 / -0.5
SiCl4 / -158.0 / 0.0 / -1.4 / -0.9 / -0.4 / -0.6
C2F4 / -157.4 / 4.9 / 3.3 / 3.4 / 3.3 / 3.3
CF3Br / -155.0 / 1.3 / -1.9 / -1.9 / -1.5 / -1.7
COF2 / -149.1 / -3.4 / -3.9 / -4.0 / -4.0 / -4.2
AlCl3 / -139.7 / 3.3 / 2.0 / 2.6 / -1.4 / -1.2
H3C=OOC=OCH3
(acetic anhydride) / -136.8 / 2.7 / 2.7 / 2.2 / 2.2 / 1.9
POCl3 / -133.8 / -2.3 / 0.2 / 0.3 / 1.1 / 0.5
CF3CN / -118.4 / 1.8 / 2.3 / 2.2 / 2.3 / 2.2
CH3C=OOCH(CH3)2
(isopropyl acetate) / -115.1 / 1.4 / 1.3 / 1.0 / 1.1 / 0.8
CF3 / -111.3 / 0.3 / 1.0 / 1.0 / 0.2 / 0.3
CH2F2 / -107.7 / 0.7 / -0.1 / 0.0 / 0.0 / 0.0
CH3COF / -105.7 / 0.1 / -0.1 / 2.5 / -0.3 / -0.5
CH3COOH / -103.4 / -0.1 / -0.1 / 5.0 / -0.4 / -0.5
CHF2Br / -101.6 / 0.4 / -2.1 / 0.8 / -1.6 / -1.8
CH3COOCH3 / -98.4 / 0.9 / 0.7 / 0.4 / 0.5 / 0.2
BCl3 / -96.3 / 0.0 / -2.5 / -1.8 / 0.8 / 0.0
SO3 / -94.6 / -1.5 / 1.1 / 0.6 / 0.0 / -0.1
CO2 / -94.1 / 1.2 / 1.9 / 1.4 / 1.5 / 1.1
MgCl2 / -93.8 / -0.3 / 1.7 / 2.0 / 0.0 / 0.0
CH3CH(OC3)2
(1,1dimethoxy ethane) / -93.1 / 1.9 / 0.4 / 0.3 / 0.3 / 0.1
HCOOH / -90.5 / 0.5 / 0.4 / 0.2 / 0.1 / 0.0
(CH3)2SO2
(dimethyl sulphone) / -89.7 / -0.3 / 0.9 / 2.6 / 1.8 / 0.3
PCl5 / -86.1 / 1.7 / 4.3 / 4.9 / 6.3 / 5.6
HCOOCH3 / -85.0 / 1.6 / 2.2 / 1.9 / 1.9 / 1.7
SO2Cl2 / -84.8 / -2.5 / 0.0 / -0.1 / 0.0 / -0.3
LiF / -80.1 / 0.7 / -0.5 / -0.3 / -0.3 / -0.9
(CH3)2CHOCH(CH3)2
(di-isopropyl ether) / -76.3 / 1.3 / -1.5 / -1.9 / -1.8 / -1.5
C4H8O2
(1.4-dioxane) / -75.5 / 1.4 / 0.8 / 0.7 / 0.6 / 0.5
(CH3)3COH
(t-butanol) / -74.7 / 0.7 / 0.2 / 0.2 / 0.2 / 0.1
C6H4F2
(1,3-difluorobenzene) / -73.9 / 0.0 / -0.7 / -0.7 / -1.0 / -0.8
C6H4F2
(1,4-difluorobenzene) / -73.3 / 0.0 / -0.8 / -0.8 / -1.0 / -0.9
SO2 / -71.0 / -3.8 / 0.4 / 0.0 / -0.5 / -0.6
NaF / -69.4 / 0.8 / 1.7 / 1.7 / 0.7 / 0.5
PCl3 / -69.0 / -3.3 / -3.7 / -3.5 / -2.7 / -3.2
(CH3)3COCH3
(t-butyl-methyl ether) / -67.8 / 1.3 / 1.0 / 1.0 / 1.1 / 0.9
(CH3)2CHOH / -65.2 / 0.5 / -0.5 / -0.5 / -0.5 / -0.6
HF / -65.1 / 0.2 / -0.6 / -0.5 / -0.5 / -0.5
AlF / -63.5 / 2.9 / 2.5 / 2.6 / -2.2 / -1.9
CH3CH2COCH2CH3
(diethyl ketone) / -61.6 / 1.1 / -0.2 / -0.6 / 0.1 / 0.3
CH3CH2OCH2CH3
(diethyl ether) / -60.3 / 0.8 / 0.4 / 0.1 / 0.1 / 0.3
CH3COCl / -58.0 / 0.2 / 0.0 / -0.2 / 0.3 / 0.0
H2O / -57.8 / -0.3 / -0.7 / -0.6 / -0.8 / -0.7
CH3COCH2CH3
(methyl ethyl ketone) / -57.1 / 0.4 / 0.8 / 0.6 / 0.7 / 0.5
CH3CONH2 / -57.0 / -1.1 / -1.4 / -1.1 / -1.4 / -1.0
CH3CH2OH / -56.2 / 0.1 / -0.2 / -0.1 / -0.2 / -0.2
Si(CH3)4
(tetramethylsilane) / -55.7 / -2.8 / -3.5 / -3.5 / -4.0 / -4.1
C5H10O
(tetrahydropyran) / -53.4 / 0.3 / 0.5 / 0.4 / 0.4 / 0.4
Cl2CO / -52.4 / 0.7 / 0.2 / 0.1 / 0.9 / 0.4
CH3COCH3 / -51.9 / 0.0 / 0.0 / -0.1 / -0.1 / -0.2
C2H5OCH3 / -51.7 / 1.1 / 1.0 / 1.0 / 1.0 / 0.9
(CH3)2CHCHO
(isobutanal) / -51.6 / -0.5 / -0.6 / -0.8 / -0.7 / -0.9
HCOCOH
(glyoxal) / -50.7 / 0.9 / 1.6 / 1.3 / 1.2 / 1.0
C8H18 (n-octane) / -49.9 / 0.2 / -0.5 / -0.1 / -0.2 / 0.0
H3COH / -48.0 / 0.1 / 0.0 / 0.1 / 0.0 / 0.0
C5H8O
(cyclopentanone) / -45.9 / 0.8 / 0.7 / 0.5 / 0.5 / 0.4
C7H16 (n-heptane) / -44.9 / 0.1 / -0.1 / -0.1 / 0.1 / 0.0
CH3OCH3 / -44.0 / 0.4 / 0.5 / 0.5 / 0.5 / 0.4
C4H8O
(tetrahydrofuran) / -44.0 / 0.5 / -1.8 / -1.5 / -1.9 / -1.6
NaCl / -43.8 / 1.3 / -0.1 / 0.0 / -0.7 / -1.0
(CH3)3CCl
(t-butyl chloride) / -43.5 / 0.6 / 0.4 / 0.5 / 1.0 / 0.8
C6H14
(methyl pentane) / -41.1 / 0.0 / -0.7 / -0.4 / -0.5 / -0.3
SiCl2 / -40.3 / -0.1 / -1.7 / -1.5 / -1.6 / -1.7
C5H12 (neopentane) / -40.2 / -0.2 / -0.8 / -1.0 / -0.6 / -1.0
C6H14
(n-hexane) / -39.9 / -0.2 / -0.3 / 0.0 / -0.1 / 0.0
CH3CHO / -39.7 / 0.1 / 0.3 / 0.2 / 0.2 / 0.1
CH3CH2CH(CH3)NO2
(nitro-s-butane) / -39.1 / 1.8 / -1.7 / -1.2 / -1.8 / -1.2
ClF3 / -38.0 / -1.9 / -1.3 / -1.2 / -0.7 / -1.0
CH3CH2CH2CH2Cl / -37.0 / -0.6 / -1.4 / -1.0 / -0.7 / -0.7
(CH3)2SO
(dimethyl sulfoxide) / -36.2 / -1.5 / 0.9 / 0.7 / 0.3 / 0.3
C6H13Br / -35.4 / 0.7 / -2.5 / -2.0 / -1.9 / -1.7
C5H12 (n-pentane) / -35.1 / -0.2 / -0.2 / -0.2 / 0.0 / -0.2
CH2=CHF / -33.2 / 1.2 / 0.9 / 0.9 / 1.0 / 0.9
OCS / -33.0 / 3.2 / 3.3 / 3.6 / 2.4 / 3.1
H2O2 / -32.5 / -0.8 / -2.0 / -1.9 / -2.2 / -2.1
C4H10
(isobutane) / -32.1 / 0.2 / -0.2 / -0.2 / 0.0 / -0.2
NF3 / -31.6 / 0.1 / -3.1 / -2.4 / -2.9 / -2.3
CH3CH2CH2Cl / -31.5 / 0.4 / -0.7 / -0.4 / -0.1 / -0.1
C4H10
(transbutane) / -30.0 / 0.4 / 0.0 / 0.0 / 0.2 / 0.0
C6H12
(cyclohexane) / -29.5 / -0.5 / -0.6 / -0.6 / -0.5 / -0.6
C6H4O2
(benzoquinone) / -29.4 / -0.3 / -0.2 / -0.6 / -0.9 / -0.9
(CH3)3CNH2
(t-butylamine) / -28.9 / 0.1 / 0.1 / 0.1 / 0.4 / 0.3
C6H5F
(fluorobenzene) / -27.7 / -0.5 / -0.8 / -0.9 / -1.1 / -0.9
COBr2 / -27.1 / 2.6 / 2.0 / 1.8 / 2.5 / 2.2
C2H5Cl / -26.8 / -0.1 / -0.6 / -0.4 / 0.0 / -0.2
CO / -26.4 / 0.3 / 0.7 / 0.5 / 0.5 / 0.4
(CH3)3CSH
(t-butanethiol) / -26.2 / 1.0 / 1.3 / 1.4 / 0.9 / 1.1
H2CO / -26.0 / 0.6 / 0.3 / 0.5 / 0.2 / 0.4
C3H8 / -25.0 / 0.3 / 0.0 / 0.0 / 0.2 / 0.0
CHCl3 / -24.7 / 0.0 / -1.3 / -0.7 / 0.0 / 0.0
SiO / -24.6 / -0.7 / -0.4 / -0.9 / -1.4 / -1.7
CH3CH=CHCHO
(crotonaldehyde) / -24.0 / 1.1 / 0.2 / 0.5 / 0.0 / 0.4
C3H7Br / -23.8 / 0.1 / -1.7 / -1.6 / -1.2 / -1.3
C6H5OH (phenol) / -23.0 / -0.9 / -1.1 / -1.2 / -1.5 / -1.3
CCl4 / -22.9 / 1.7 / -1.0 / -0.1 / 0.9 / 0.8
CH2Cl2 / -22.8 / -0.5 / -1.0 / -0.7 / 0.0 / -0.2
HCl / -22.1 / -0.1 / -1.0 / -0.8 / -0.4 / -0.6
C2H6 / -20.1 / 0.3 / 0.1 / 0.1 / 0.2 / 0.1
CH3Cl / -19.5 / -0.1 / -0.3 / -0.1 / 0.3 / 0.1
C5H10
(cyclopentane) / -18.3 / -0.8 / -0.9 / -0.9 / -0.8 / -0.8
CH3CH2SSCH2CH3
(diethyl disulfide) / -17.9 / -0.6 / 0.0 / 0.1 / -1.1 / -0.6
CH4 / -17.9 / 0.3 / 0.2 / 0.1 / 0.3 / 0.2
CH3NO2 / -17.8 / 0.0 / 0.2 / 0.6 / 0.0 / 0.5
HOCl / -17.8 / -0.4 / -1.2 / -1.0 / -0.8 / -0.8
C3H6Br2 / -17.1 / 2.2 / -0.6 / -0.4 / 0.2 / 0.2
CH3ONO / -15.9 / -0.2 / -1.5 / -1.2 / -1.7 / -1.3
C5H10S
(tetrahydrothiopyran) / -15.2 / 0.0 / 0.6 / 0.5 / 0.0 / 0.3
C2H5Br / -14.8 / 0.9 / -0.6 / -0.5 / -0.1 / -0.2
FCl / -13.2 / -0.7 / -1.3 / -1.1 / -0.8 / -0.9
C5H8Br2 / -13.1 / 3.1 / -2.4 / -2.1 / -1.6 / -1.6
C2H4O (oxirane) / -12.6 / 0.0 / -0.8 / -0.6 / -0.9 / -0.7
CH2CO / -11.4 / 0.8 / 1.6 / 1.3 / 1.4 / 1.2
CH3CH2NH2 / -11.3 / 0.0 / 0.3 / 0.3 / 0.6 / 0.5
Cyc-C5H10NH
(piperidine) / -11.3 / -0.7 / -0.6 / -0.6 / -0.4 / -0.4
C2H5SH
(ethanethiol) / -11.1 / -0.4 / 0.1 / 0.1 / -0.4 / -0.2
NH3 / -11.0 / -0.8 / -0.4 / -0.4 / -0.2 / -0.2
CCl3Br / -10.0 / 2.2 / 0.3 / 1.1 / 2.0 / 2.1
CH3SCH3 / -8.9 / 0.0 / 0.8 / 0.9 / 0.4 / 0.5
C4H4O (furan) / -8.3 / -0.5 / -0.2 / -0.3 / -0.5 / -0.5
C4H8S
(tetrahydrothiophene) / -8.2 / -0.4 / 0.1 / 0.2 / -0.4 / -0.2
CH3SiH3 / -7.0 / -0.2 / 3.5 / 3.5 / 2.9 / 2.9
(CH3)3N / -5.7 / 0.2 / 0.7 / 0.6 / 1.0 / 0.9
CH3SH / -5.5 / -0.3 / 0.2 / 0.2 / -0.4 / -0.1
CH3NH2 / -5.5 / -1.0 / -0.4 / -0.5 / -0.2 / -0.3
ClFO3 / -5.1 / -5.0 / -2.8 / -3.2 / -2.8 / -3.4
H2S / -4.9 / -0.2 / -0.5 / -0.4 / -1.1 / -0.8
(CH3)2NH / -4.4 / -0.9 / 1.5 / 1.3 / -1.2 / -1.1
SCl2 / -4.2 / -1.9 / -4.1 / -3.8 / -3.8 / -3.8
H2COH / -4.1 / -0.1 / 0.0 / 0.1 / -0.3 / -0.1
C4H8 (isobutane) / -4.0 / 0.0 / 0.1 / 0.1 / 0.2 / 0.1
S2Cl2 / -4.0 / 0.5 / -1.6 / -1.4 / -1.9 / -1.7
CH3CH2O (2A'') / -3.7 / 0.1 / 0.7 / 0.6 / 0.1 / 0.2
C4H6O (divinyl ether) / -3.3 / -0.1 / 0.3 / 0.1 / 0.1 / 0.0
C2Cl4 / -3.0 / 3.4 / 1.7 / 2.7 / 3.4 / 3.6
CH3CO (2A') / -2.4 / 0.1 / 1.0 / 0.8 / 0.2 / 0.6
C4H8NH
(tetrahydropyrrole) / -0.8 / -0.6 / -0.5 / 0.3 / -0.3 / -0.1
F2 / 0.0 / -0.7 / -3.1 / -2.7 / -3.0 / -2.8
H2 / 0.0 / 0.5 / 0.4 / 0.4 / 0.5 / 0.4
Cl2 / 0.0 / -1.1 / -3.4 / 3.1 / -2.4 / -2.6
O2 / 0.0 / -1.1 / -3.6 / 3.6 / -3.6 / -3.5
N2 / 0.0 / -2.1 / -0.4 / 0.5 / -0.3 / -0.2
SO / 1.2 / -0.5 / 1.9 / 1.9 / -2.4 / -2.1
PH3 / 1.3 / -1.8 / 1.8 / 1.8 / 1.6 / 1.4
N2O4 / 2.2 / 1.6 / 1.6 / 0.3 / 1.0 / 0.1
ClNO2 / 2.9 / 1.0 / 1.0 / 0.3 / 1.2 / 0.4
CH3O / 4.1 / -0.1 / 0.3 / 0.3 / 0.1 / 0.1
CH3CH=CH2 / 4.8 / 0.0 / 0.1 / 0.2 / 0.1 / 0.2
(CH3)2CHCN
(isobutane nitrile) / 5.6 / -0.5 / 0.2 / 0.0 / 0.2 / 0.2
F2O / 5.9 / -0.8 / -6.6 / -6.0 / -6.7 / -6.2
C4H8 (cyclobutane) / 6.8 / 0.0 / -0.1 / 0.0 / 0.0 / 0.0
NO2 / 7.9 / -0.2 / -0.5 / 0.2 / -1.1 / -0.6
SiH4 / 8.2 / 0.9 / 1.6 / 1.7 / 1.0 / 1.1
CH2=CHCl / 8.9 / 3.6 / 3.5 / 3.6 / 4.0 / 3.9
OH / 9.4 / 1.0 / 0.5 / 0.6 / 0.5 / 0.5
HCO / 10.0 / 0.3 / 1.0 / 0.7 / 0.7 / 0.5
C6H5CH3 (toluene) / 12.0 / -0.3 / -0.1 / -0.2 / -0.3 / -0.2
(CH3)3C / 12.3 / -0.9 / 0.0 / 0.0 / -0.7 / -0.6
C6H5Cl
(chlorobenzene) / 12.4 / 0.1 / 0.0 / 0.0 / 0.2 / 0.2
ClNO / 12.4 / -0.5 / -1.6 / -2.3 / -1.3 / -2.0
C2H4 / 12.5 / 0.1 / -1.6 / -1.7 / -1.6 / -1.6
C3H6
(cyclopropane) / 12.7 / -0.8 / -0.7 / -0.7 / -0.7 / -0.7
P4 / 14.1 / -1.5 / 1.6 / 1.5 / 0.0 / -0.1
CH3C=OCCH
(acetyl acetylene) / 15.6 / -1.9 / -1.1 / -1.4 / -1.4 / -1.5
C5H8 (isoprene) / 18.0 / -0.3 / 0.3 / 0.2 / 0.3 / 0.3
CH3CN / 18.0 / 1.0 / 0.6 / 0.4 / 0.6 / 0.5
C2H3Br / 18.9 / 1.9 / 1.2 / 1.3 / 1.6 / 1.6
Si2H6 / 19.1 / 2.2 / 1.9 / 1.9 / 0.5 / 0.7
N2O / 19.6 / 0.7 / 2.1 / 1.5 / 2.1 / 1.7
C2H4S / 19.6 / 1.0 / 1.3 / 1.3 / 0.7 / 1.0
C6H6 / 19.7 / -0.6 / -0.5 / -0.5 / -0.7 / -0.5
N2O3 / 19.8 / 0.7 / 0.0 / -0.9 / -0.4 / -1.0
C5H6S
(2-methylthiophene) / 20.0 / 0.6 / 1.3 / 1.3 / 0.6 / 0.9
C4H6S
(2.5-dihydrothiophene) / 20.8 / 0.7 / 1.4 / 1.4 / 0.7 / 1.0
C6H5NH2 (aniline) / 20.8 / -0.4 / 0.1 / 0.0 / 0.0 / 0.2
(CH3)2CH (2A') / 21.5 / -0.1 / 0.5 / 0.5 / 0.1 / 0.2
NO / 21.6 / 0.1 / -0.8 / -1.0 / -1.0 / -1.1
NH2NH2 / 22.8 / -1.4 / -1.0 / -1.0 / -0.7 / -0.7
ClO / 24.2 / -1.6 / -2.0 / -2.0 / -1.9 / -2.0
C5H7N / 24.6 / 0.2 / 0.4 / 0.2 / 0.3 / 0.4
C6H8
(1.4-cyclo
hexadiene) / 25.0 / -1.2 / -0.9 / -0.9 / -1.0 / -0.9
C6H5Br / 25.2 / 1.4 / 0.0 / 0.1 / 0.2 / 0.3
C6H8
(1,3-cyclohexadiene) / 25.4 / -0.8 / -1.4 / -1.4 / -1.5 / -1.4
C4H5N (pyrrole) / 25.9 / -0.8 / -0.1 / -0.2 / -0.2 / -0.1
CH2CHCHCH2 / 26.3 / -0.3 / 0.3 / 0.2 / 0.2 / 0.2
C4H4S / 27.5 / 0.2 / 0.8 / 0.7 / 0.0 / 0.3
CS2 / 28.0 / 3.3 / 4.9 / 4.4 / 3.5 / 3.6
C2H5 (2A') / 28.9 / 0.0 / 0.4 / 0.4 / 0.3 / 0.3
CH3S (2A') / 29.8 / 1.0 / 1.5 / 1.5 / 0.7 / 1.0
C2H4NH / 30.2 / -0.8 / -0.6 / -0.7 / -0.5 / -0.5
S2 / 30.7 / -0.3 / -0.5 / -0.5 / -1.9 / -1.3
HCN / 31.5 / 0.9 / 1.3 / 1.1 / 1.2 / 1.2
ClCN / 32.9 / 1.6 / 1.8 / 1.9 / 1.8 / 1.7
PH2 / 33.1 / 0.9 / 2.3 / 2.3 / 2.2 / 2.0
LiH / 33.3 / 0.5 / -0.4 / 0.1 / -0.2 / -0.5
C5H5N (pyridine) / 33.6 / 0.2 / 0.5 / 0.4 / 0.3 / 0.5
Na2 / 34.0 / 4.5 / 2.1 / 2.1 / 0.0 / -0.4
O3 / 34.1 / -0.4 / -2.2 / -2.6 / -2.7 / -3.0
HS / 34.2 / 0.5 / 0.8 / 0.9 / 0.4 / 0.6
P2 / 34.3 / 0.0 / -0.5 / -0.7 / -1.3 / -1.4
C4H6 (2-butyne) / 34.8 / -0.2 / 0.8 / 0.7 / 0.8 / 0.7
CH3 / 35.0 / 0.6 / 0.8 / 0.8 / 1.0 / 0.9
C10H8 (naphthalene) / 35.9 / 0.8 / 1.4 / 1.2 / 0.9 / 1.2
C4H6 (cyclobutene) / 37.4 / -1.9 / -1.6 / -1.6 / -1.7 / -1.6
CH3-CH=C=CH2
(methyl allene) / 38.8 / 0.2 / 1.1 / 0.8 / 0.7 / 1.1
CH2CHCN / 43.2 / -0.7 / 0.2 / 0.0 / 0.1 / 0.1
LiNa / 43.4 / 3.8 / 0.1 / 1.9 / -0.8 / 0.0
CH3CCH / 44.2 / 0.1 / 0.9 / 0.8 / 0.9 / 0.8
C5H8
(spiropentane) / 44.3 / -0.3 / 0.0 / 0.0 / 0.0 / 0.0
NH2 / 45.1 / 0.8 / 0.6 / 0.6 / 0.9 / 0.9
CH2=C=CH2 (allene) / 45.5 / 0.5 / 1.4 / 1.4 / 1.4 / 1.3
C4H4N2 (pyrazine) / 46.8 / -2.0 / -1.6 / -1.6 / -1.7 / -1.5
C4H4N2 (pyrimidine) / 46.9 / 2.4 / 3.1 / 3.1 / 3.0 / 3.2
SiH3 / 47.9 / 1.4 / 1.6 / 1.6 / 1.1 / 1.1
C4H6
(methylene
cyclopropane) / 47.9 / 1.6 / 2.1 / 2.1 / 2.1 / 2.1
NCCH2CH2CN / 50.1 / 1.6 / 2.7 / 2.7 / 2.6 / 2.6
Li2 / 51.6 / 2.6 / 1.3 / 1.3 / 1.5 / 0.0
C4H6 (bicyclobutane) / 51.9 / -2.4 / -2.2 / -2.2 / -2.2 / -2.1
C2H2 / 54.2 / -0.3 / 0.1 / 0.1 / 0.0 / 0.2
SiH2 (1A1) / 65.2 / 2.4 / 2.1 / 2.1 / 1.4 / 1.5
C3H4
(cyclopropene) / 66.2 / -2.2 / -1.6 / -1.6 / -1.7 / -1.6
SC / 66.9 / 1.3 / 1.0 / 1.0 / 0.3 / 0.2
C10H8 (azulene) / 69.1 / -1.5 / -1.6 / -1.6 / -2.1 / -1.1
C8H8
(cyclooctatetraene) / 70.7 / -1.0 / -0.1 / -0.1 / -0.5 / -0.3
NCCN / 73.3 / 1.6 / 2.7 / 2.7 / 1.7 / 1.6
C2H3(2A1) / 76.1 / 1.2 / 1.8 / 1.8 / 2.6 / 2.6
C6H5 (phenyl radical) / 81.2 / -1.2 / -0.3 / -0.3 / -1.6 / -0.8
BeH / 81.7 / -0.7 / 0.3 / 0.3 / 0.0 / 0.0
NH / 85.2 / 1.1 / -1.6 / -1.6 / -0.9 / -0.8
SiH2 (3B1) / 86.2 / 1.5 / -0.3 / -0.3 / -0.4 / -0.3
CH2 (3B1) / 93.7 / 1.3 / -0.4 / -0.4 / 0.2 / 0.2
CH2(1A1) / 102.8 / 1.0 / 1.3 / 1.3 / 1.3 / -0.4
CN / 104.9 / 0.1 / 0.0 / 0.0 / -0.1 / -1.3
CCH / 135.1 / -0.1 / 2.5 / 2.5 / 2.3 / 2.1
Si2 / 139.9 / 2.0 / 1.1 / 1.1 / -0.6 / -0.2
CH / 142.5 / 1.5 / -1.5 / -1.5 / -1.3 / -1.3
a) Data from references 1 and 2.
b) Calculations carried out with G3X-CEP and EnAt1
c) Calculations carried out with G3X(CCSD)-CEP and EnAt2.
Table S.4: Experimental and calculated ionization energies (in kcal mol-1) for the G3/05 test set for compounds containing elements of the first and second period of the periodic table. G3X, G3X-CEP, G3X(CCSD)-CEP, EnAt1 and EnAt2 are the differences between the experimental data and the G3X, G3X-CEP, G3X(CCSD)-CEP, G3X-CEP+EnAt1 and G3X(CCSD)-CEP+EnAt2 calculations, respectively.
Species / Exp(a) / ΔG3X / ΔG3X-CEP / ΔG3X(CCSD)-CEP / ΔEnAt1(b) / ΔEnAt2(c)H / 313.6 / -0.6 / -1.1 / -1.1 / -0.7 / -0.8
He / 566.9 / 0.0 / -0.7 / -0.7 / -0.2 / -0.2
Li / 124.3 / -0.1 / 0.7 / 0.7 / 1.1 / 1.0
Be / 214.9 / -3.6 / -3.4 / -3.3 / -2.9 / -2.9
B / 191.4 / 1.6 / -1.1 / -1.1 / 1.1 / 1.0
C / 259.7 / 1.1 / 0.4 / 0.4 / 0.8 / 0.8
N / 335.3 / 0.8 / 0.3 / 0.3 / 0.8 / 0.7
O / 313.4 / 1.0 / 0.3 / 0.3 / 0.8 / 0.8
F / 401.7 / 0.3 / 0.2 / 0.2 / 0.7 / 0.7
Ne / 497.2 / -0.9 / -4.4 / -4.3 / -3.9 / -3.9
Na / 118.5 / 0.6 / 3.3 / 3.3 / 3.7 / 3.7
Mg / 176.3 / -3.7 / -0.6 / -0.5 / -0.1 / -0.1
Al / 138.0 / 0.6 / -1.5 / -1.5 / -1.0 / -1.0
Si / 187.9 / 0.6 / -0.3 / -0.3 / 0.1 / 0.1
P / 241.9 / 0.6 / -2.8 / -2.8 / -2.4 / -2.4
S / 238.9 / 1.7 / 0.6 / 0.6 / 1.1 / 1.1
Cl / 299.1 / 1.4 / 0.7 / 0.8 / 1.2 / 1.3
Ar / 363.4 / 1.2 / -0.9 / -0.8 / -0.4 / -0.4
Sec-C3H7 / 170.0 / -2.1 / -3.7 / -3.7 / -2.8 / -2.9
CH2SH / 173.8 / 0.8 / 2.3 / 2.3 / 2.9 / 2.8
H2COH (2A1) / 174.2 / 0.4 / -4.2 / -4.2 / -3.6 / -3.6
Si2H5 / 175.3 / -2.1 / -2.4 / -2.4 / -1.8 / -1.8
N2H3 / 175.5 / 0.1 / -0.7 / -0.7 / -0.1 / -0.1
C6H5NH2 (aniline) / 178.0 / -1.6 / -1.0 / -1.0 / -1.9 / -1.6
Si2H4 / 186.6 / -1.4 / -0.1 / -0.1 / 0.2 / 0.2
C2H5 (2A´) / 187.2 / -1.0 / -1.8 / -1.8 / -1.2 / -1.3
SiH3 / 187.6 / -0.4 / 0.4 / 0.4 / 0.7 / 0.7
CHO / 187.7 / -0.1 / -0.7 / -0.7 / -0.2 / -0.2
Si2H2 / 189.1 / -1.2 / 1.7 / 1.7 / 2.1 / 2.1
C4H5N (pyrrole) / 189.3 / -0.7 / 1.0 / 1.0 / 0.7 / 0.8
C6H5OH (phenol) / 196.2 / -1.4 / -0.7 / -0.7 / -1.6 / -1.3
C6H5CH3 (toluene) / 203.6 / -1.4 / -0.4 / -0.4 / -1.8 / -1.5
C4H4O (furan) / 203.6 / -2.1 / -0.9 / -0.9 / -0.8 / -0.6
C2H4S (thiirane) / 208.7 / -0.1 / 2.7 / 2.7 / 2.7 / 2.8
SiH2 / 211.0 / -1.0 / -0.5 / -0.5 / 0.1 / 0.1
C6H6 / 213.2 / -1.2 / -0.8 / -0.8 / -1.4 / -1.2
S2 / 215.8 / 0.1 / -0.3 / -0.3 / 0.0 / 0.0
CH2S / 216.2 / 0.3 / -0.1 / -0.1 / 0.2 / 0.2
CH3SH / 217.7 / 0.8 / -0.5 / -0.5 / -0.2 / -0.2
N2H2 / 221.1 / -0.8 / -0.8 / -0.8 / -0.4 / -0.4
C3H4
(cyclopropene) / 223.0 / 0.2 / 0.2 / 0.2 / 0.1 / 0.2
CH2CCH2 / 223.5 / -0.6 / 0.0 / 0.0 / -0.8 / -0.7
B2H4 / 223.7 / 2.5 / -0.9 / -0.9 / 2.5 / 2.5
Si2H6 / 224.6 / 1.7 / 2.2 / 2.2 / 2.4 / 2.4
PH2 / 226.5 / 0.1 / 3.2 / 3.2 / 3.5 / 3.5
CH3 / 227.0 / -0.2 / -0.2 / -0.2 / 0.1 / 0.1
PH3 / 227.6 / -0.3 / 0.0 / 0.0 / 0.5 / 0.4
CS2 / 232.2 / -1.0 / -2.6 / -2.6 / -2.5 / -2.4
PH / 234.1 / -0.8 / 1.2 / 1.2 / 1.8 / 1.7
NH3 / 234.8 / 0.7 / 0.4 / 0.4 / 1.0 / 0.9
CH3CHO / 235.9 / -0.4 / -0.8 / -0.8 / -0.7 / -0.7
SH / 238.1 / 1.0 / -0.6 / -0.6 / -0.3 / -0.3
CH2 / 239.7 / 0.2 / 1.7 / 1.7 / 2.3 / 2.2
SH2 (2B1) / 241.4 / 0.7 / 0.0 / 0.0 / 0.6 / 0.5
C2H5OH / 241.4 / 1.3 / -2.1 / -2.1 / -2.1 / -2.0
C2H4 / 242.4 / -0.6 / 1.0 / 1.0 / 1.3 / 1.3
P2 / 242.8 / -0.8 / -1.8 / -1.8 / -1.4 / -1.4
CH3O / 247.3 / 0.7 / -1.0 / -1.0 / -0.4 / -0.4
CH3OH / 250.4 / -1.1 / 1.2 / 1.2 / 1.4 / 1.5
SiH4 / 253.7 / -1.0 / -1.2 / -1.2 / -0.7 / -0.7
NH2 / 256.9 / 0.4 / 1.5 / 1.5 / 1.8 / 1.8
OCS / 257.7 / -0.2 / -0.7 / -0.7 / -0.6 / -0.5
CH3Cl / 258.7 / -0.6 / -1.3 / -1.3 / -1.0 / -1.0
SC / 261.3 / -1.2 / -1.9 / -1.9 / -1.4 / -1.4
CH3OF / 261.5 / -1.2 / -2.4 / -2.4 / -2.4 / -2.3
C2H2 / 262.9 / -0.6 / -0.7 / -0.7 / -0.2 / -0.2
CF2 / 263.3 / -0.6 / 0.6 / 0.6 / 0.6 / 0.7
Cl2 / 265.2 / -0.4 / 0.3 / 0.3 / 0.5 / 0.5
BCl3 / 267.5 / -2.7 / 1.8 / 1.8 / 1.5 / 1.7
B2F4 / 278.3 / 6.9 / 3.2 / 3.2 / 2.4 / 2.7
O2 / 278.3 / -0.5 / -0.8 / -0.8 / -0.8 / -0.7
CH3F / 287.6 / -2.9 / 1.4 / 1.4 / 1.7 / 1.7
H2O / 291.0 / 0.5 / -0.1 / -0.1 / 0.4 / 0.4
CH4 / 291.0 / -2.2 / -3.1 / -3.1 / -2.6 / -2.6
ClF / 291.1 / -0.2 / -0.9 / -0.9 / -0.7 / -0.7
HOF / 293.1 / -0.6 / -1.6 / -1.6 / -1.3 / -1.3
HCl / 294.0 / 0.6 / 1.1 / 1.1 / 1.6 / 1.6
OH / 300.0 / 1.6 / 1.8 / 1.8 / 2.1 / 2.1
NCCN / 308.3 / -1.5 / 0.3 / 0.3 / 0.3 / 0.4
NH / 312.6 / 0.0 / 1.5 / 1.5 / 1.5 / 1.6
CN / 313.6 / -6.5 / -0.5 / -0.5 / -0.1 / -0.1
CO2 / 317.6 / -0.1 / -1.3 / -1.3 / -1.2 / -1.1
CO / 323.1 / -0.5 / -1.0 / -1.0 / -0.6 / -0.6
BF3 / 358.8 / -3.8 / -2.6 / -2.6 / -2.8 / -2.7
N2 (2Σcation) / 359.3 / -0.4 / -0.1 / -0.1 / 0.3 / 0.3
HF / 369.9 / -0.2 / -0.3 / -0.3 / 0.2 / 0.2
a) Data from references 1 and 2.
b) Calculations carried out with G3X-CEP and EnAt1.
c) Calculations carried out with G3X(CCSD)-CEP and EnAt2.
Table S.5: Experimental and calculated electron affinities (in kcal mol-1) for the G3/05 test set for compounds containing elements of the first and second period of the periodic table. G3X, G3X-CEP, G3X(CCSD)-CEP, EnAt1 and EnAt2 are the differences between the experimental data and the G3X, G3X-CEP, G3X(CCSD)-CEP, G3X-CEP+EnAt1 and G3X(CCSD)-CEP+EnAt2 calculations, respectively.
Species / Exp(a) / ΔG3X / ΔG3X-CEP / ΔG3X(CCSD)-CEP / ΔEnAt1(b) / ΔEnAt2(c)Li / 14.3 / -3.3 / -3.4 / -3.5 / -3.9 / -3.9
B / 6.4 / 1.7 / 0.9 / 0.9 / 0.5 / 0.6
C / 29.1 / 1.6 / 1.0 / 1.0 / 0.6 / 0.6
O / 33.7 / 2.4 / 2.0 / 2.0 / 1.5 / 1.5
F / 78.4 / -0.5 / -0.8 / -0.9 / -1.3 / -1.3
Na / 12.6 / -4.0 / -3.6 / -3.6 / -4.1 / -4.1
Al / 10.2 / 1.2 / 0.8 / 0.8 / 0.4 / 0.4
Si / 31.9 / 0.2 / -0.3 / -0.3 / -0.7 / -0.7
P / 17.2 / 0.4 / -0.3 / -0.3 / -0.8 / -0.9
S / 47.9 / -0.2 / 0.5 / 0.5 / 0.0 / 0.0
Cl / 83.4 / -0.3 / 0.4 / 0.3 / -0.1 / -0.1
NO / 0.5 / 0.5 / -1.1 / -1.1 / -1.1 / -1.2
CH3 / 1.8 / 3.3 / 1.9 / 1.9 / 1.4 / 1.4
CF2 / 4.1 / 0.0 / -0.2 / -0.2 / -1.1 / -1.0
HCO / 7.2 / 0.0 / -0.1 / -0.1 / -0.4 / -0.4
HNO / 7.8 / 1.4 / 0.0 / 0.0 / -0.6 / -0.6
LiH / 7.9 / -1.5 / -1.0 / -1.0 / -1.1 / -1.2
NH / 8.8 / 4.2 / 3.0 / 3.0 / 2.1 / 2.2
CH3CO / 9.8 / 0.3 / 0.8 / 0.8 / 0.8 / 0.7
O2 / 10.1 / 1.5 / 0.0 / 0.0 / -0.9 / -0.8
CH2S / 10.7 / 0.2 / 0.0 / 0.0 / -0.6 / -0.5
CH2CHCH2 / 10.9 / 0.0 / 1.2 / 1.2 / 1.1 / 1.1
HCF / 12.5 / 0.4 / 0.5 / 0.5 / -0.1 / -0.1
CH2 / 15.0 / 1.9 / -0.2 / -0.2 / -0.5 / -0.5
C2H3 / 15.4 / 0.2 / -0.5 / -0.5 / -0.8 / -0.8
NH2 / 17.8 / 1.8 / 0.6 / 0.6 / 0.0 / 0.1
H2CCCH / 20.6 / -0.4 / 0.3 / 0.3 / -2.7 / -2.6
PH / 23.8 / 1.0 / 0.7 / 0.7 / 0.4 / 0.4
CH2NC / 24.4 / -1.9 / -2.4 / -2.4 / -2.5 / -2.6
HO2 / 24.9 / 0.3 / -1.1 / -1.1 / -1.3 / -1.3
PO / 25.1 / 1.2 / -0.9 / -0.9 / -0.9 / -1.0
SO2 / 25.5 / -0.7 / -0.3 / -0.3 / -1.2 / -1.1
SiH2 / 25.9 / 1.2 / 1.6 / 1.6 / 1.3 / 1.3
CH / 28.6 / 1.5 / 0.5 / 0.5 / -0.2 / -0.1
PH2 / 29.3 / 0.0 / -0.1 / -0.1 / -0.6 / -0.5
SiH / 29.4 / 0.1 / 0.6 / 0.6 / 0.6 / 0.5
SiH3 / 32.5 / -0.3 / 0.2 / 0.2 / -0.3 / -0.3
CH2CN / 35.6 / 0.5 / 0.0 / 0.0 / -0.1 / -0.2
CH3O / 36.2 / 0.9 / 0.4 / 0.4 / 0.2 / 0.2
S2 / 38.3 / -0.1 / 0.0 / 0.0 / -0.6 / -0.6
CH3CH2O / 39.5 / -1.1 / -1.1 / -1.1 / -1.0 / -1.1
H2CCC / 41.4 / -0.4 / 0.3 / 0.3 / -0.4 / -0.3
CH2CHO / 42.1 / 0.0 / -0.8 / -0.8 / -0.8 / -0.9
OH / 42.2 / 1.1 / -0.3 / -0.3 / -0.8 / -0.8
CH3S / 43.1 / 0.1 / -0.8 / -0.8 / -1.0 / -1.1
S2O / 43.3 / -1.5 / -0.2 / -0.2 / -1.1 / -1.0
CH3CH2S / 45.0 / -2.5 / -0.6 / -0.6 / -0.5 / -0.6
O3 / 48.5 / 0.3 / -0.4 / -0.4 / -1.3 / -1.2
OF / 52.4 / 0.1 / -1.4 / -1.4 / -1.6 / -1.7
NO2 / 52.4 / -0.4 / -1.2 / -1.2 / -1.2 / -1.3
C2O / 52.8 / 0.0 / 0.1 / 0.1 / -0.6 / -0.5
CHCO / 54.2 / 0.7 / -0.8 / -0.8 / -0.9 / -1.0
HS / 54.4 / 0.8 / 1.2 / 1.2 / 0.6 / 0.7
Cl2 / 55.1 / -0.9 / -1.7 / -1.7 / -2.4 / -2.3
C2H / 68.5 / 1.0 / 1.9 / 1.9 / 1.4 / 1.4
C2 / 75.5 / 2.7 / -0.2 / -0.2 / -0.6 / -0.6
NCO / 83.2 / 0.4 / -0.8 / -0.8 / -0.9 / -1.0
CN / 89.0 / -0.8 / -3.1 / -3.1 / -3.5 / -3.5
a) Data from references 6, 12 and 13.
b) Calculations carried out with G3X-CEP and EnAt1
c) Calculations carried out with G3X(CCSD)-CEP and EnAt2.
Table S.6: Experimental and calculated proton affinities (in kcal mol-1) for the G3/05 test set. G3X, G3X-CEP, G3X(CCSD)-CEP, EnAt1 and EnAt2 are the differences between the experimental data and the G3X, G3X-CEP, G3X(CCSD)-CEP, G3X-CEP+EnAt1 and G3X(CCSD)-CEP+EnAt2 calculations, respectively.
Molecules / Exp(a) / ΔG3X / ΔG3X-CEP / ΔG3X(CCSD)-CEP / ΔEnAt1(b) / ΔEnAt2(c)H2O / 165.1 / 1.8 / 1.6 / 1.6 / 1.6 / 1.6
NH3 / 202.5 / -0.5 / -0.7 / -0.7 / -0.7 / -0.7
C2H2 / 152.3 / 0.1 / 3.9 / 3.9 / 3.9 / 3.9
H2 / 100.8 / 1.2 / 1.2 / 1.2 / 1.2 / 1.2
HCl / 133.6 / 0.8 / 0.7 / 0.7 / 0.7 / 0.7
PH3 / 187.1 / 1.7 / -0.5 / -0.5 / -0.5 / -0.5
SH2 / 168.8 / 1.4 / 1.4 / 1.3 / 1.4 / 1.3
SiH4 / 154.0 / 2.2 / 1.9 / 1.9 / 1.9 / 1.9
a) Data from references 1 and 2.
b) Calculations carried out with G3X-CEP and EnAt1
c) Calculations carried out with G3X(CCSD)-CEP and EnAt2.
Table S.7: Experimental and calculated atomization energy (D0) for the G3/05 test set (data in kcal mol-1) for molecules containing non-transition third-row elements. G3X, G3X-CEP, G3X(CCSD)-CEP, EnAt1 and EnAt2 are the differences between the experimental data and the G3X, G3X-CEP, G3X(CCSD)-CEP, G3X-CEP+EnAt1 and G3X(CCSD)-CEP+EnAt2 calculations, respectively.
Species / Exp(a) / ΔG3X / ΔG3X-CEP / ΔG3X(CCSD)-CEP / ΔEnAt1(b) / ΔEnAt2(c)D0 / As2 / 91.3 / -1.6 / 0.3 / 0.2 / 0.1 / 0.2
AsH2 / 131.1 / -1.2 / -1.3 / -1.4 / 1.6 / 1.4
AsH3 / 206.0 / 0.8 / 0.9 / 0.8 / 0.7 / 0.9
AsH / 64.6 / -0.4 / 0.2 / 0.1 / 0.6 / 0.3
BrF / 58.9 / -0.2 / 0.1 / -0.3 / 0.5 / 0.6
BrCl / 51.5 / 0.5 / 2.5 / 2.1 / 1.9 / 1.9
Br2 / 45.4 / 0.1 / -0.5 / -0.9 / 1.1 / 1.1
BBr / 103.5 / 1.1 / 1.7 / 1.5 / 1.3 / 1.4
BrO / 55.3 / -0.1 / 1.6 / 1.2 / 1.2 / 1.2
CH3Br / 358.2 / -0.1 / 0.8 / 0.6 / 0.4 / 0.5
GaCl / 109.9 / -1.3 / -2.6 / -2.9 / 3.0 / 3.0
GeH4 / 270.5 / -2.8 / 1.5 / 1.4 / 1.3 / 1.5
GeO / 155.2 / -3.0 / -3.2 / -3.4 / 3.5 / 3.5
GeS2 / 191.7 / -2.5 / 1.9 / 1.6 / 1.4 / 1.4
HBr / 86.5 / 0.0 / 0.2 / 0.0 / 1.4 / 1.4
K2 / 12.6 / -2.2 / -1.4 / -1.4 / 1.4 / 1.3
KBr / 90.5 / 0.0 / 0.3 / 0.2 / 1.4 / 1.3
KCl / 101.0 / 0.3 / 0.3 / 0.1 / 0.0 / 0.0
KrF2 / 21.9 / -1.3 / 4.7 / 4.0 / 3.7 / 3.6
NaBr / 86.2 / -1.9 / -0.3 / -0.4 / 0.6 / 0.5
SeH / 74.3 / -1.1 / -1.4 / -1.5 / 1.7 / 1.6
SeH2 / 153.2 / 0.6 / 0.0 / -0.1 / 0.2 / 0.1
IE0 / K / 100.1 / 0.8 / 6.4 / 6.4 / 6.8 / 6.8
Ca / 140.9 / -2.1 / 2.6 / 2.7 / 3.1 / 3.1
Ga / 138.3 / -0.2 / 0.7 / 0.7 / 1.1 / 1.0
Ge / 182.2 / -0.1 / 2.2 / 2.2 / 2.6 / 2.6
As / 225.7 / -0.3 / -0.6 / -0.6 / -0.2 / -0.2
Se / 224.9 / 0.5 / 1.9 / 2.0 / 2.4 / 2.4
Br / 272.4 / 0.0 / 1.2 / 1.3 / 1.7 / 1.7
Kr / 322.8 / 0.9 / 2.5 / 2.6 / 3.1 / 3.1
AsH2 / 217.8 / -0.8 / 0.2 / 0.2 / 0.5 / 0.5
AsH / 222.3 / -1.0 / 0.2 / 0.2 / 0.2 / 0.2
Br2 / 242.6 / -0.2 / 1.8 / 1.8 / 2.0 / 2.0
BrF / 271.1 / 0.8 / 0.8 / 0.8 / 1.1 / 1.1
HBr / 268.9 / 0.8 / 2.2 / 2.2 / 2.8 / 2.7
NaBr / 191.6 / -5.1 / -2.6 / -2.6 / -2.1 / -2.1
HOBr / 245.3 / -0.6 / 0.0 / 0.0 / 0.2 / 0.3
SeH / 227.0 / -0.1 / 0.9 / 0.9 / 1.8 / 1.7
SeH2 / 228.0 / -0.4 / 1.3 / 1.3 / 1.8 / 1.8
EA0 / K / 11.5 / -3.0 / -1.4 / -1.5 / -1.9 / -1.9
Ge / 28.4 / -0.4 / 0.9 / 0.9 / 0.5 / 0.5
Br / 77.6 / -0.9 / 1.3 / 1.2 / 0.8 / 0.8
BrO / 54.4 / -1.2 / 1.6 / 1.2 / 1.2 / 1.2
SeH / 51.0 / -0.5 / -1.4 / -1.5 / 1.7 / 1.7
PA0 / CH3Br / 157.3 / 0.4 / -0.6 / -0.6 / -0.6 / -0.6
Br - / 322.6 / 0.3 / -0.9 / -0.9 / -0.9 / -0.9
a) Data from references 1 and 2.
b) Calculations carried out with G3X-CEP and EnAt1
c) Calculations carried out with G3X(CCSD)-CEP and EnAt2.
1