Towards Accurate Thermochemistry of First Row Transition ... · Table S1. Atomic ROHF‐ccCA‐TM...

Towards Accurate Thermochemistry of First Row Transition Metal Complexes

Wanyi Jiang, Nathan J. DeYonker, John J. Determan, Angela K. Wilson*

Center for Advanced Scientific Computing and Modeling (CASCaM), Department of Chemistry, University of North Texas, Denton, TX 76203-5070.

Table S1. Atomic ROHF‐ccCA‐TM energies in Hartrees

Method H B C N O FHF/aug‐cc‐pVTZ‐DK ‐0.499828 ‐24.534878 ‐37.701737 ‐54.426849 ‐74.855775 ‐99.486979HF/aug‐cc‐pVQZ‐DK ‐0.499955 ‐24.535661 ‐37.703251 ‐54.429532 ‐74.860377 ‐99.494249

HF/CBS‐DK ‐0.499986 ‐24.535851 ‐37.703619 ‐54.430185 ‐74.861499 ‐99.496021

MP2/aug‐cc‐pVDZ‐DK 0.000000 ‐0.040757 ‐0.057987 ‐0.077514 ‐0.116608 ‐0.159455MP2/aug‐cc‐pVTZ‐DK 0.000000 ‐0.048689 ‐0.072740 ‐0.100460 ‐0.154553 ‐0.211759MP2/aug‐cc‐pVQZ‐DK 0.000000 ‐0.051696 ‐0.077712 ‐0.107749 ‐0.167748 ‐0.230737

MP2/CBS‐DK + HF/CBS‐DK ‐0.499986 ‐24.589305 ‐37.784182 ‐54.542067 ‐75.036854 ‐99.737778

MP2/cc‐pVTZ‐DK ‐0.499816 ‐24.583103 ‐37.773418 ‐54.525426 ‐75.006350 ‐99.692174CCSD(T)/cc‐pVTZ‐DK ‐0.499816 ‐24.604802 ‐37.795621 ‐54.543766 ‐75.026080 ‐99.707330

CCSD(T)/aug‐cc‐pCVDZ‐DK ‐0.499341 ‐24.598590 ‐37.781042 ‐54.517950 ‐74.980342 ‐99.640303CCSD(T,FC1)/aug‐cc‐pCVDZ‐DK ‐0.499341 ‐24.634179 ‐37.817537 ‐54.555299 ‐75.018343 ‐99.678974

(CC) 0.000000 ‐0.021698 ‐0.022204 ‐0.018340 ‐0.019730 ‐0.015156(CV) 0 000000 ‐0 035589 ‐0 036496 ‐0 037349 ‐0 038000 ‐0 038671(CV) 0.000000 0.035589 0.036496 0.037349 0.038000 0.038671ccCA‐TM energy ‐0.499986 ‐24.646592 ‐37.842881 ‐54.597756 ‐75.094584 ‐99.791606Spin‐orbit correction 0 ‐0.000046 ‐0.000135 0 ‐0.000355 ‐0.000614Total ccCA‐TM energy ‐0.499986 ‐24.646638 ‐37.843016 ‐54.597756 ‐75.094939 ‐99.792220

Experimental Atomic Hf (0K) in kcal mol‐1 51.63 135.1 170.1123 112.53 58.99 18.47

Experimental 0K ‐ 298.15K correction in kcal mol‐1 1.01 0.29 0.25 1.04 1.04 1.05

2


MethodHF/aug‐cc‐pVTZ‐DKHF/aug‐cc‐pVQZ‐DK

HF/CBS‐DK

MP2/aug‐cc‐pVDZ‐DKMP2/aug‐cc‐pVTZ‐DKMP2/aug‐cc‐pVQZ‐DK

MP2/CBS‐DK + HF/CBS‐DK

MP2/cc‐pVTZ‐DKCCSD(T)/cc‐pVTZ‐DK

CCSD(T)/aug‐cc‐pCVDZ‐DKCCSD(T,FC1)/aug‐cc‐pCVDZ‐DK

(CC)(CV)

Al Si P S Cl‐242.311159 ‐289.455576 ‐341.532144 ‐398.583753 ‐460.888456‐242.312498 ‐289.457541 ‐341.534694 ‐398.586835 ‐460.892033

‐242.312824 ‐289.458020 ‐341.535316 ‐398.587585 ‐460.892905

‐0.035164 ‐0.051046 ‐0.068105 ‐0.098110 ‐0.128487‐0.040433 ‐0.061233 ‐0.084677 ‐0.127511 ‐0.169988‐0.042643 ‐0.064903 ‐0.089884 ‐0.137729 ‐0.185471

‐242.356778 ‐289.525051 ‐341.628145 ‐398.731205 ‐461.087406

‐242.351167 ‐289.516000 ‐341.615653 ‐398.708851 ‐461.054635‐242.367125 ‐289.536533 ‐341.637418 ‐398.736249 ‐461.083375

‐242.359007 ‐289.522976 ‐341.614977 ‐398.696980 ‐461.028986‐242.576342 ‐289.738625 ‐341.844457 ‐398.929786 ‐461.265455

‐0.015958 ‐0.020533 ‐0.021765 ‐0.027397 ‐0.028740‐0 217335 ‐0 215649 ‐0 229480 ‐0 232806 ‐0 236469(CV)

ccCA‐TM energySpin‐orbit correctionTotal ccCA‐TM energy

Experimental Atomic Hf (0K) in kcal mol‐1

Experimental 0K ‐ 298.15K correction in kcal mol‐1

0.217335 0.215649 0.229480 0.232806 0.236469‐242.590071 ‐289.761233 ‐341.879390 ‐398.991408 ‐461.352615

‐0.00034 ‐0.000682 0 ‐0.000892 ‐0.00134‐242.590411 ‐289.761915 ‐341.879390 ‐398.992300 ‐461.353955

80.2 107.15 75.42 65.66 28.59

1.08 0.76 1.28 1.05 1.1

3



HF/CBS‐DK





(CC)(CV)

Sc Ti V Cr Mn‐763.280926 ‐852.739392 ‐948.131894 ‐1049.649743 ‐1157.373198‐763.281259 ‐852.739859 ‐948.132498 ‐1049.650481 ‐1157.374232

‐763.281340 ‐852.739973 ‐948.132645 ‐1049.650660 ‐1157.374484

‐0.027519 ‐0.036706 ‐0.053073 ‐0.083150 ‐0.107202‐0.030644 ‐0.042705 ‐0.063184 ‐0.096018 ‐0.126587‐0.031559 ‐0.044492 ‐0.066337 ‐0.101241 ‐0.133953

‐763.313408 ‐852.785464 ‐948.200763 ‐1049.754988 ‐1157.512746

‐763.311188 ‐852.780803 ‐948.192710 ‐1049.743793 ‐1157.495647‐763.323349 ‐852.795632 ‐948.210406 ‐1049.752716 ‐1157.514447

‐763.322418 ‐852.794018 ‐948.208598 ‐1049.751747 ‐1157.512397‐763.598322 ‐853.088907 ‐948.516391 ‐1050.067313 ‐1157.828123

‐0.012161 ‐0.014828 ‐0.017696 ‐0.008923 ‐0.018800‐0 275903 ‐0 294888 ‐0 307793 ‐0 315566 ‐0 315727(CV)




0.275903 0.294888 0.307793 0.315566 0.315727‐763.601472 ‐853.095181 ‐948.526253 ‐1050.079477 ‐1157.847273

‐0.00046 ‐0.001014 ‐0.001455 0 0‐763.601932 ‐853.096195 ‐948.527708 ‐1050.079477 ‐1157.847273

90.17 112.55 122.4 94.49 67.42

1.24 1.15 1.11 0.97 1.19

4



HF/CBS‐DK





(CC)(CV)

Fe Co Ni Cu Zn‐1271.325924 ‐1391.855175 ‐1519.069478 ‐1653.121619 ‐1794.231116‐1271.327213 ‐1391.856756 ‐1519.071412 ‐1653.123472 ‐1794.232913

‐1271.327527 ‐1391.857141 ‐1519.071884 ‐1653.123924 ‐1794.233352

‐0.162446 ‐0.220833 ‐0.287561 ‐0.463804 ‐0.467897‐0.193447 ‐0.261363 ‐0.341711 ‐0.527089 ‐0.535523‐0.206268 ‐0.279528 ‐0.365597 ‐0.557616 ‐0.569129

‐1271.541391 ‐1392.147549 ‐1519.451758 ‐1653.699993 ‐1794.822866

‐1271.513019 ‐1392.107790 ‐1519.399475 ‐1653.629164 ‐1794.746548‐1271.532842 ‐1392.121619 ‐1519.403714 ‐1653.581684 ‐1794.719333

‐1271.528812 ‐1392.116735 ‐1519.397968 ‐1653.579198 ‐1794.713982‐1271.851057 ‐1392.439434 ‐1519.716760 ‐1653.893896 ‐1795.020058

‐0.019823 ‐0.013829 ‐0.004238 0.047480 0.027214‐0 322245 ‐0 322699 ‐0 318792 ‐0 314698 ‐0 306076(CV)




0.322245 0.322699 0.318792 0.314698 0.306076‐1271.883458 ‐1392.484076 ‐1519.774787 ‐1653.967210 ‐1795.101727

‐0.001836 ‐0.003614 ‐0.004428 0 0‐1271.885294 ‐1392.487690 ‐1519.779215 ‐1653.967210 ‐1795.101727

98.73 101.6 102.3 80.4 31.04

1.08 1.14 1.14 1.2 1.36

5



HF/CBS‐DK





(CC)(CV)

Ga Ge As Se Br‐1942.125647 ‐2096.990044 ‐2258.940619 ‐2427.969319 ‐2604.295286‐1942.129255 ‐2096.994863 ‐2258.945824 ‐2427.974861 ‐2604.301223

‐1942.130134 ‐2096.996037 ‐2258.947093 ‐2427.976211 ‐2604.302670

‐0.032076 ‐0.044243 ‐0.056865 ‐0.080305 ‐0.102200‐0.036852 ‐0.054098 ‐0.072440 ‐0.108275 ‐0.142686‐0.039572 ‐0.057473 ‐0.077270 ‐0.118076 ‐0.157351

‐1942.171379 ‐2097.055450 ‐2259.027088 ‐2428.099944 ‐2604.468533

‐1942.162014 ‐2097.043406 ‐2259.012026 ‐2428.075575 ‐2604.434779‐1942.175414 ‐2097.059516 ‐2259.028744 ‐2428.097439 ‐2604.458185

‐1942.091193 ‐2096.969411 ‐2258.929207 ‐2427.979142 ‐2604.321656‐1942.630515 ‐2097.504778 ‐2259.462486 ‐2428.509873 ‐2604.850348

‐0.013400 ‐0.016110 ‐0.016719 ‐0.021864 ‐0.023406‐0 539323 ‐0 535367 ‐0 533278 ‐0 530731 ‐0 528692(CV)




0.539323 0.535367 0.533278 0.530731 0.528692‐1942.724102 ‐2097.606928 ‐2259.577085 ‐2428.652539 ‐2605.020631

‐0.00251 ‐0.004415 0 ‐0.004305 ‐0.005597‐1942.726612 ‐2097.611343 ‐2259.577085 ‐2428.656844 ‐2605.026228

65 89.94 68.745 54.25 26.74

1.566 1.77 1.48 1.48 1.48

6

Table S2. Atomic UHF‐ccCA‐TM energies in Hartrees

Method H B C N O FHF/aug‐cc‐pVTZ‐DK ‐0.499828 ‐24.538909 ‐37.706765 ‐54.430383 ‐74.865147 ‐99.493750HF/aug‐cc‐pVQZ‐DK ‐0.499955 ‐24.539737 ‐37.708339 ‐54.433107 ‐74.869913 ‐99.501171

HF/CBS‐DK ‐0.499986 ‐24.539939 ‐37.708723 ‐54.433771 ‐74.871074 ‐99.502979

MP2/aug‐cc‐pVDZ‐DK 0.000000 ‐0.037073 ‐0.053712 ‐0.075018 ‐0.110427 ‐0.154726MP2/aug‐cc‐pVTZ‐DK 0.000000 ‐0.044409 ‐0.067765 ‐0.097528 ‐0.146399 ‐0.205395MP2/aug‐cc‐pVQZ‐DK 0.000000 ‐0.047250 ‐0.072539 ‐0.104671 ‐0.159181 ‐0.224076

MP2/CBS‐DK + HF/CBS‐DK ‐0.499986 ‐24.588856 ‐37.784003 ‐54.542491 ‐75.037651 ‐99.737931

MP2/cc‐pVTZ‐DK ‐0.499816 ‐24.582890 ‐37.773458 ‐54.525885 ‐75.007156 ‐99.692401CCSD(T)/cc‐pVTZ‐DK ‐0.499816 ‐24.604834 ‐37.795723 ‐54.543973 ‐75.026213 ‐99.707393

CCSD(T)/aug‐cc‐pCVDZ‐DK ‐0.499341 ‐24.598621 ‐37.781121 ‐54.518115 ‐74.980448 ‐99.640347CCSD(T,FC1)/aug‐cc‐pCVDZ‐DK ‐0.499341 ‐24.634192 ‐37.817547 ‐54.555309 ‐75.018344 ‐99.678971

(CC) 0.000000 ‐0.021943 ‐0.022265 ‐0.018088 ‐0.019057 ‐0.014992(CV) 0.000000 ‐0.035571 ‐0.036427 ‐0.037194 ‐0.037896 ‐0.038623ccCA‐TM energy ‐0.499986 ‐24.646371 ‐37.842694 ‐54.597773 ‐75.094604 ‐99.791546Spin‐orbit correction 0 ‐0.000046 ‐0.000135 0 ‐0.000355 ‐0.000614Total ccCA‐TM energy ‐0.499986 ‐24.646417 ‐37.842829 ‐54.597773 ‐75.094959 ‐99.792160

Experimental Atomic Hf (0K) in kcal mol‐1 51.63 135.1 170.1123 112.53 58.99 18.47

Experimental 0K ‐ 298.15K correction in kcal mol‐1 1.01 0.29 0.25 1.04 1.04 1.05

7



HF/CBS‐DK

Al Si P S Cl‐242.315188 ‐289.460021 ‐341.532506 ‐398.591968 ‐460.896079‐242.316552 ‐289.461999 ‐341.535080 ‐398.595172 ‐460.899784

‐242.316885 ‐289.462481 ‐341.535707 ‐398.595952 ‐460.900687


‐0.031341 ‐0.047109 ‐0.068064 ‐0.091936 ‐0.122820‐0.036103 ‐0.056676 ‐0.084408 ‐0.118795 ‐0.162004‐0.038133 ‐0.060166 ‐0.089578 ‐0.128628 ‐0.177155



‐242.356225 ‐289.524675 ‐341.628214 ‐398.730298 ‐461.086730

‐242.350914 ‐289.515928 ‐341.615731 ‐398.708221 ‐461.054215‐242.367210 ‐289.536671 ‐341.637499 ‐398.736398 ‐461.083570


(CC)(CV)

‐242.359104 ‐289.523148 ‐341.615133 ‐398.697234 ‐461.029227‐242.576377 ‐289.738654 ‐341.844461 ‐398.929816 ‐461.265471

‐0.016296 ‐0.020743 ‐0.021768 ‐0.028177 ‐0.029355‐0.217273 ‐0.215506 ‐0.229328 ‐0.232582 ‐0.236244


‐242.589795 ‐289.760924 ‐341.879311 ‐398.991058 ‐461.352329‐0.00034 ‐0.000682 0 ‐0.000892 ‐0.00134

‐242.590135 ‐289.761606 ‐341.879311 ‐398.991950 ‐461.353669


Experimental 0K ‐ 298.15K correction in kcal mol‐180.2 107.15 75.42 65.66 28.59

1.08 0.76 1.28 1.05 1.1

8



HF/CBS‐DK

Sc Ti V Cr Mn‐763.285073 ‐852.746662 ‐948.140057 ‐1049.649963 ‐1157.376513‐763.286117 ‐852.748142 ‐948.141425 ‐1049.650758 ‐1157.377671

‐763.286371 ‐852.748502 ‐948.141758 ‐1049.650951 ‐1157.377953


‐0.026751 ‐0.035840 ‐0.051650 ‐0.083177 ‐0.104827‐0.029663 ‐0.041335 ‐0.061372 ‐0.096046 ‐0.124042‐0.030509 ‐0.042954 ‐0.064415 ‐0.101263 ‐0.131320



‐763.317350 ‐852.792359 ‐948.207894 ‐1049.755297 ‐1157.513528

‐763.314359 ‐852.786720 ‐948.199118 ‐1049.744039 ‐1157.496563‐763.326280 ‐852.801467 ‐948.216729 ‐1049.752958 ‐1157.515177


(CC)(CV)

‐763.325571 ‐852.799636 ‐948.214553 ‐1049.752021 ‐1157.513145‐763.598356 ‐853.089026 ‐948.516646 ‐1050.067688 ‐1157.828706

‐0.011921 ‐0.014747 ‐0.017611 ‐0.008919 ‐0.018614‐0.272784 ‐0.289391 ‐0.302093 ‐0.315667 ‐0.315561


‐763.602055 ‐853.096496 ‐948.527598 ‐1050.079883 ‐1157.847703‐0.00046 ‐0.001014 ‐0.001455 0 0

‐763.602515 ‐853.097510 ‐948.529053 ‐1050.079883 ‐1157.847703



1.24 1.15 1.11 0.97 1.19

9



HF/CBS‐DK

Fe Co Ni Cu Zn‐1271.337142 ‐1391.867165 ‐1519.079576 ‐1653.122181 ‐1794.231116‐1271.338860 ‐1391.869389 ‐1519.082083 ‐1653.124036 ‐1794.232914

‐1271.339278 ‐1391.869931 ‐1519.082693 ‐1653.124487 ‐1794.233352


‐0.158839 ‐0.217855 ‐0.285373 ‐0.463433 ‐0.467897‐0.188669 ‐0.257529 ‐0.338993 ‐0.526689 ‐0.535523‐0.201194 ‐0.275443 ‐0.362708 ‐0.557178 ‐0.569129



‐1271.547908 ‐1392.156115 ‐1519.459581 ‐1653.700094 ‐1794.822866

‐1271.519405 ‐1392.115910 ‐1519.406825 ‐1653.629372 ‐1794.746548‐1271.536852 ‐1392.128261 ‐1519.410220 ‐1653.581760 ‐1794.719333


(CC)(CV)

‐1271.532638 ‐1392.122888 ‐1519.403989 ‐1653.579278 ‐1794.713982‐1271.851563 ‐1392.439838 ‐1519.717049 ‐1653.893912 ‐1795.020058

‐0.017447 ‐0.012351 ‐0.003395 0.047611 0.027214‐0.318925 ‐0.316951 ‐0.313059 ‐0.314635 ‐0.306076


‐1271.884280 ‐1392.485416 ‐1519.776035 ‐1653.967117 ‐1795.101727‐0.001836 ‐0.003614 ‐0.004428 0 0

‐1271.886116 ‐1392.489030 ‐1519.780463 ‐1653.967117 ‐1795.101727



1.08 1.14 1.14 1.2 1.36

10



HF/CBS‐DK

Ga Ge As Se Br‐1942.128854 ‐2096.994002 ‐2258.941859 ‐2427.976791 ‐2604.301995‐1942.132603 ‐2096.998906 ‐2258.947074 ‐2427.982464 ‐2604.308088

‐1942.133517 ‐2097.000101 ‐2258.948345 ‐2427.983846 ‐2604.309573


‐0.029078 ‐0.040947 ‐0.056509 ‐0.075422 ‐0.097798‐0.033540 ‐0.050316 ‐0.071806 ‐0.100908 ‐0.135882‐0.036091 ‐0.053569 ‐0.076607 ‐0.110353 ‐0.150230



‐1942.171179 ‐2097.055545 ‐2259.027667 ‐2428.099702 ‐2604.468185

‐1942.161961 ‐2097.043628 ‐2259.012640 ‐2428.075574 ‐2604.434630‐1942.175626 ‐2097.060009 ‐2259.029489 ‐2428.097837 ‐2604.458342


(CC)(CV)

‐1942.091407 ‐2096.969889 ‐2258.929911 ‐2427.979602 ‐2604.321882‐1942.630537 ‐2097.504806 ‐2259.462505 ‐2428.509900 ‐2604.850361

‐0.013664 ‐0.016381 ‐0.016849 ‐0.022263 ‐0.023711‐0.539131 ‐0.534918 ‐0.532594 ‐0.530298 ‐0.528480


‐1942.723974 ‐2097.606844 ‐2259.577111 ‐2428.652262 ‐2605.020376‐0.00251 ‐0.004415 0 ‐0.004305 ‐0.005597

‐1942.726484 ‐2097.611259 ‐2259.577111 ‐2428.656567 ‐2605.025973


Experimental 0K ‐ 298.15K correction in kcal mol‐165 89.94 68.745 54.25 26.74

1.566 1.77 1.48 1.48 1.48

11

12

Table S3. The ground states and experimental values of Hf (298 K) in kcal mol‐1 for the test set of 225

molecules. The values of Hf (298 K) are calculated by adding theoretical corrections from ccCA‐TM

when only Hf (0 K) or dissociation energies are available. Experimental data is rounded to the first

decimal digit. Selected theoretical Hf‘s are also listed in square brackets. Alternative experimental values are also given below the selected one. (Experimental data for metal dimers is given in Table S4.)

Molecule Ground State

Exp. Hf (298 K) d

B3LYP a ROHF b Exp. [Theor.] c ScH 1 (C∞v) 1+( C∞v)

e 93.7 e ScN 1 (C∞v) 1+( C∞v)

e 91.0 ± 20 f ScO 2 (C∞v) 2+( C∞v)

e ‐13.0 ± 2.2 g ScS 2 (C∞v) [2+( C∞v)

h] 41.7 ± 3.1 g ScSe 2 (C∞v) [2+( C∞v)

h] 53.0 ± 4.1 g ScF 1 (C∞v) [1+( C∞v)

e] ‐33.9 ± 3.4 i ‐33.99 ± 4.1 g ScB2

2A1 (C2v) 2A1 (C2v) 150.6 ± 21 g

ScC2 2A1 (C2v)

2A1 (C2v) [2A1 (C2v) j,k] 152.7 ± 4.0 g

ScF2 (D∞h) 2 Ag (D2h) [2 g

+(D∞h) l] ‐163.7 ± 5.3 i

‐157.4 ± 7.0 g ScF3

1A' (Cs) [1A1' (D3h) m] ‐300.4 ± 3.6 i

‐302.9 ± 3.2 g ScCl3

1A' (Cs) [1A1' (D3h) n] ‐160.5 ± 2.1 g

ScBr3 1A1' (D3h) [1A1' (D3h)

n] ‐109.3 ± 2.6 g ScC4

2A1 (C2v) 2A1 (C2v) [2A1 (C2v)

k] 196.2 ± 5.0 g Sc2O

1A1 (C2v) ‐4.5 ± 11 g 2.81 ± 18 o (ScCl3)2

1Ag (D2h) 1Ag (D2h) ‐369.0 ± 8 g

Sc(C5H5)3 1A' (C3h)

1A' (Cs) 20.0 ± 1.4 p

TiH (C∞v)

4B1 (C2v) 4( C∞v) e 116.4 ± 2.3 q

TiB (C∞v) 6A1 (C2v) 181.3 ± 15 g

TiC 3 (C∞v) 3A1 (C2v) [3+( C∞v) e] 169.8 g

TiN 2 (C∞v) 2A1 (C2v) 2+( C∞v)

e 112.0 ± 7.0 g TiO (C∞v)

3A1 (C2v) X3( C∞v) r, [X3( C∞v) s] 13.7 ± 2.2 g TiS (C∞v)

3A1 (C2v) 3t, [3C∞v) h] 76.2 ± 2.2 g

79.0 u TiSe (C∞v)

3A2 (C2v) [3C∞v) h] 76.8 ± 10 g 81.2 u TiF 4(C∞v) 4B1 (C2v) [4( C∞v) e] ‐4.0 ± 8.0 g ‐16.0 ± 10 r TiCl (C∞v)

4B1 (C2v) 4( C∞v) v , 4(C∞v) r 40.9 ± 2.0 w

24.2 g 36.9 ± 10 r TiBr 4(C∞v) 4B1 (C2v)

4( C∞v) v, 4(C∞v) r 50.8 ± 10 r 35.0 g

13


Exp. Hf (298 K) d

B3LYP a ROHF b Exp. [Theor.] c TiC2

3B1 (C2v) 3B2 (C2v) [3B1 (C2v)

x,y] 175.4 ± 3.0 g TiO2

1A1 (C2v) (C2v) r, [1A1( C2v)

s] ‐73.0 ± 3.0 r ‐67.9 z ‐71.0 ± 5.1 g TiF2 (D∞h)

3Ag (D2h) (D∞h) r, [3g(D∞h)

l, 3g or3g

‐(D∞h) aa ] ‐164.5 ± 10 r

‐180 ± 10 g TiCl2 (D∞h)

3Ag (D2h) (D∞h) r, [3g(D∞h)

l,aa ] ‐49.0 ± 2.0 w ‐57.0 ± 3.0 g ‐56.7 ± 3.0 r TiBr2 (D∞h)

3Ag (D2h) (D∞h) r, 3g ‐42.8 ± 5.0 r

TiF3 2A1' (D3h)

2A1 (C2v) (C3v) r ‐284.0 ± 10 r

‐283.8 g TiCl3

2A1' (D3h) 2A1 (C2v) (C3v)

r ‐121.5 ± 2.0 w ‐129.4 ± 1.3 g ‐128.9 ± 1.5 r TiBr3

2A1' (D3h) 2A1 (C2v) (C3v)

r ‐89.6 ± 2.5 r ‐89.6 g TiC4

3A1 (C2v) 3A1 (C2v) [3A1 (C2v)

y ] 217.9 ± 5.0 g TiF4

1A1 (Td) (Td) r, [1A1 (Td)

m] ‐370.8 ± 0.5 g ‐371.0 ± 1.0 r TiCl4

1A1 (Td) (Td) r ‐182.4 ± 0.7 g

‐182.4 ± 0.9 r TiBr4

1A1 (Td) (Td) r ‐131.0 ± 0.2 g

‐131.5 ± 1.2 r TiOF 2A' (Cs)

2A' (Cs) (C∞v) r ‐103.5 g,r

TiOCl 2A' (Cs) 2A' (Cs) (C∞v)

r ‐58.4 g,r TiOF2

1A (C1) (C2v) r ‐221.1 g,r

TiOCl2 1A1 (C2v) (C2v)

r ‐130.4 g,r [‐142.9 ± 4.8] bb TiCl3Br

1A1 (C3v) ‐169.8 g TiCl2Br2

1A1 (C2v) ‐157.2 g TiClBr3

1A1 (C3v) ‐144.6 g (TiCl3)2

1Ag (D2h) ‐301.0 g Ti(C5H5)Cl3

1A' (Cs) [1A' (Cs) cc] ‐124.6 ± 1.6 p

14


Exp. Hf (298 K) d

B3LYP a ROHF b Exp. [Theor.] c VH (C∞v)

5A1 (C2v) 5C∞v) e 124.9 ± 1.6 dd VC (C∞v)

2A1 (C2v) [2( C∞v) e] 181.6 ± 15 g VN (C∞v)

3A2 (C2v) 3(C∞v) r 121.0 ± 3.0 g

125.0 ± 5.0 r VO 4(C∞v) 4A2 (C2v) X4‐ (C∞v)

r 31.8 ± 2.0 ee 30.5 ± 5.0 r 36.2 ± 10 g VS 4(C∞v) 4A2 (C2v) [4‐C∞v) h] 80.4 ± 3.2 g VSe 4(C∞v) 4A2 (C2v) [4‐C∞v) h] 96.2 g VF (C∞v)

5B1 (C2v) 5C∞v) e 0.7 ± 15 g

VCl (C∞v) 5A2 (C2v) 49.7 ± 2.0 ff

37.9 ± 1.5 g VBr (C∞v)

5A1 (C2v) 46.2 ± 10 g VC2

4B1 (C2v) 4B1 (C2v) [4B1 (C2v)

gg] 184.1 ± 5.0 g VO2

2A1(C2v) 2A' (Cs) (C2v)

r,ee, [ 2A1(C2v) ii,kk] ‐41.6 ± 3.3 ee

‐55.6 ± 10 r ‐54.8 ± 5.0 g VCl2

4g (D∞h)

4B1g (D2h) [4g‐(D∞h)

l, (D∞h) ff] ‐34.8 ± 2.0 ff

‐51.6 ± 3.6 g VBr2

4g (D∞h) 4B1g (D2h)

4g‐ ‐36.5 g

VCl3 3A" (Cs)

3A" (Cs) (D3h) ff ‐85.6 ± 2.0 ff

‐88.2 ± 2.1 g VBr3

3B2 (C2v) 3B1 (C2v) ‐61.6 g

VC4 4B1 (C2v)

4B1 (C2v) [4B1 (C2v) gg] 232.4 ± 5.0 g

VCl4 2A (C2)

2A (D2) (Td) ff ‐126.1 ± 0.6 ff

‐125.7 ± 0.6 g VBr4

2B1 (D2d) 2A1 (C2v) ‐84.0 g

VF5 1A1' (D3h) [1A1'(D3h)

m] ‐343.2 ± 0.2 g VOCl3

1A1 (C3v) ‐166.4 ± 1.3 g VO(OH)3

1A' (Cs) ‐250.0 g VBrCl3

2A' (Cs) 2A' (Cs) ‐119.4 g

V4O10 1A1 (Td)

[1A1 (Td) hh] ‐675.0 ± 5.0 g

15


Exp. Hf (298 K) d

B3LYP a ROHF b Exp. [Theor.] c CrH 6(C∞v) 6A1 (C2v)

6+C∞v) p 101.7 ± 1.6 dd 80.2 ± 10 g CrGe (C∞v)

7B1 (C2v) [5(C∞v) jj] 144.1 ± 7.1 g

CrN 4(C∞v) 4A2 (C2v) 4(C∞v) r 120.7 ± 5.0 r

112.0 ± 15 g CrO (C∞v)

5B1 (C2v) X3‐or X5 (C∞v) r [5(C∞v) ll] 43.6 ± 1.6 mm

45.5 ± 7.0 g 45.0 ± 10 r CrS (C∞v)

5B1 (C2v) [5C∞v) h] 78.4 ± 5.1 g CrF 6(C∞v) 6A1 (C2v)

6+(C∞v) e, 6+(C∞v)

ll,nn 4.6 ± 2.4 oo 8.2 ± 10 g

[‐3.1 ± 2.4] ll [‐2.6] nn CrCl 6(C∞v) 6A1 (C2v) 6+(C∞v)

nn 31.1 ± 0.7 oo 33.7 ± 1.6 pp

36.4 g CrBr 6(C∞v) 6A1 (C2v) 44.6 ± 6.0 g CrC2

5B1 (C2v) 5A1 (C2v) [5A1 (C2v)

qq] 186.4 ± 5.0 g CrO2

3B1 (C2v) 3B1 (C2v) (C2v)

r, [ 3B1(C2v) ii,rr] ‐23.7 ± 1.2 mm

‐18.0 ± 10 r ‐14.5 ± 15 g CrF2

5B2 (C2v) 5B2 (C2v) (D∞h)

oo [5g(D∞h) l, 5B2(C2v)

nn] ‐103.2 ± 3.0 oo ‐99.1 ± 4.2 g ‐106.7 nn CrCl2

5B2 (C2v) 5B2 (C2v) (C2v)

oo, [5g(D∞h) l, 5B2(C2v)

nn] ‐28.1 ± 0.4 oo ‐26 .3 ± 1.0 pp ‐32.1 ± 2.2 g CrBr2

5B2 (C2v) 5B2 (C2v) ‐14.1 ± 4.3 g

CrO3 1A1 (C3v) (D3h)

r, [ 1A1(C3v) rr] ‐77.3 ± 1.0 mm

‐70.5 ± 20 g ‐70.0 ± 10 r [‐62.3] z CrF3

4B2 (C2v) 4B2 (C2v) (D3h)

oo ‐199.8 ± 3.4 oo ‐216.6 ± 3.2 g CrCl3

4A (C3v) 4A (C1) (D3h)

ss ‐67.6 ± 1.5 oo CrCl4

3A1 (Td) 3A (D2) (Td)

ss ‐94.8 ± 3.3 oo ‐107.0 ± 3.0 g CrBr4

3A1 (Td) 3A (D2) ‐51.3 ± 4.5 g

16


Exp. Hf (298 K) d

B3LYP a ROHF b Exp. [Theor.] c CrOH 6A' (Cs)

6A' (Cs) (Cs) mm [6A' (Cs)

tt,rr] 18.9 ± 1.8 mm CrOF 4A'' (Cs)

4A'' (Cs) (Cs) oo ‐73.3 ± 1.9 oo

CrOF2 1A1 (C2v) (C2h)

oo ‐153.3 ± 3.4 oo ‐148.0 ± 12 g CrOCl2

1A1 (C2v) (C2h) oo ‐80.4 ± 5.4 oo

‐74.0 ± 12 g CrO2Cl

2A' (Cs) 2A' (Cs) (C2h)

oo ‐74.2 ± 5.2 oo ‐74.0 ± 12 g CrClFO2

1A' (Cs) ‐161.2 g CrO2F2

1A1 (C2v) (C2v) oo ‐201.6 ± 5.0 oo

CrO2Cl2 1A1 (C2v) (C2v)

oo ‐124.1 ± 1.0 oo ‐126.4 g Cr(OH)2

3A" (Cs) (C2h) mm [5B (C2)

tt, rr] ‐76.8 ± 1.2 mm ‐78.1 ± 2.6 oo CrO2(OH)2

1A (C1) ‐181.6 ± 1.7 uu ‐178.8 ± 1.0 mm ‐176.0 g (CrCl2)2

9B1 (C2v) 9B1 (C2v) ‐116.9 ± 8.0 g

(CrBr2)2 9B1 (C2v)

9B1 (C2v) ‐79.8 ± 8.0 g (CrO3)3

1A1 (C3v) ‐389.0 ± 10 g

‐356.8 z Cr(CO)3

1A1 (C3v) [1A1 (C3v) vv] ‐44.0 ± 10 p

Cr(CO)4 1A1 (C2v) [1A1 (C2v)

vv] ‐102.0 ± 6.0 p Cr(CO)5

1A1 (C4v) [1A1 (C4v) vv] ‐153.9 ± 3.1 p

Cr(CO)6 1A1g (Oh) [(Oh)

ww] ‐240.0 ± 1.1 g ‐218.0 ± 20 p MnH 7(C∞v) 7A1 (C2v)

7+C∞v) p 87.3 ± 4.6 xx 64.2 g MnO 6(C∞v) 6A1 (C2v) [6+( C∞v)

e] 29.6 ± 3.0 g MnS 6(C∞v) 6A1 (C2v) [6+C∞v) h] 63.3 ± 2.0 g MnSe 6(C∞v) 6A1 (C2v) [6+C∞v) h] 73.0 ± 4.0 g MnF 7(C∞v) 7A1 (C2v)

6+( C∞v) e, 7+(C∞v)

nn ‐19.9 ± 3.0 g ‐14.5 ± 4.0 yy ‐20.1 ± 5.0 zz MnCl 7(C∞v) 7A1 (C2v) 7+(C∞v)

nn 15.8 ± 1.6 pp 11.3 g MnBr 7(C∞v) 7A1 (C2v)

7+ 20.1 g

17


Exp. Hf (298 K) d

B3LYP a ROHF b Exp. [Theor.] c MnF2

6g (D∞h)

6Ag (D2h) [6g+ (D∞h)

l,nn] ‐126.2 ± 1.0 g ‐127.0 ± 7.0 zz MnCl2

6g (D∞h)

6Ag (D2h) [6g+ (D∞h)

l,nn] ‐62.6 ± 1.0 pp ‐63.0 ± 0.5 g MnBr2

6g (D∞h)

6Ag (D2h) [6g+ (D∞h)

aaa] ‐41.9 ± 3.0 g MnF3

5A1 (C2v) 5A1 (C2v) ‐188.0 ± 14 g, zz

MnF4 4A2 (D2d)

4A2 (C2v) 4A2 (D2d)

bbb ‐231.0 ± 17 g, zz MnOH 7A' (Cs)

7A' (Cs) 3.3 ± 3.2 g (MnCl2)2

11B2 (C2v) 11B2 (C2v) ‐168.2 ± 4.0 g

(MnCl2)2 11B2 (C2v)

11B2 (C2v) ‐123.9 ± 6.0 g Mn(CO)5

2A1 (C4v) 2A1 (C2v) ‐179.4 ± 1.2 g

‐171.0 ± 5.3 p Mn(CO)5H

1A1 (C4v) ‐176.8 ± 2.2 p Mn(CO)5Cl

1A1 (C4v) ‐219.5 ± 3.1 p Mn(CO)5Br

1A (C4v) ‐210.9 ± 2.2 p Mn(CO)3(C5H5)

1A' (Cs) ‐102.0 ± 0.7 p

‐114.2 ± 0.2 ccc FeH (C∞v)

4A1 (C2v) 4( C∞v) e 113.9 ± 1.9 ddd

FeO 5(C∞v) 5A2 (C2v) 5(C∞v) r 61.1 ± 3.0 g

60.0 ± 5.0 r FeS 5(C∞v) 5A1 (C2v) [5+C∞v) h] 88.6 ± 3.9 r 83.8 ± 5.0 g FeF (C∞v)

6A2 (C2v) 6(C∞v) r, 6(C∞v) nn 11.4 ± 5.0 r

FeCl (C∞v) 6A1 (C2v) 6(C∞v) nn,eee 49.5 ± 1.6 pp

45 g 60 ± 20 r FeBr 6(C∞v) 6A1 (C2v) [6(C∞v) fff] 69.1 ± 20 g FeF2

5g (D∞h) 5Ag (D2h) (D∞h)

r, [5g(D∞h) l,nn] ‐93.1 ± 3.4 r

‐82.4 g FeCl2

5g (D∞h) 5Ag (D2h)

5 (D∞h) r, [5g(D∞h)

l,nn,eee] ‐32.8 ± 1.0 pp ‐31.7 ± 0.2 g ‐33.7 ± 0.5 r FeBr2

5g (D∞h) 5Ag (D2h) (D∞h)

r ‐9.9 ± 0.5 r ‐10.5 ± 0.6 g

18


Exp. Hf (298 K) d

B3LYP a ROHF b Exp. [Theor.] c FeF3

6A1 (C2v) 6A1 (C2v) (D3h)

r ‐178.2 g ‐196.2 ± 5.0 r FeCl3 6A' (Cs)

6A1 (C2v) (D3h) r, [6A1'(D3h)

eee] ‐60.6 ± 1.0 g ‐60.5 ± 1.2 r FeBr3 (D3h)

6A1 (C2v) ‐30.0 ± 1.0 g Fe(OH)2

5Ag (C2h) 5Ag (C2h) (C2h)

r ‐79.0 ± 0.5 r ‐79.5 ± 3.0 g (FeCl2)2

9B2 (C2v) 9B2 (C2v) (D2h)

r ‐103.1 ± 1.0 r ‐98.5 ± 3.0 g (FeBr2)2

9B2 (C2v) (D2h) r ‐60.5 ± 1.9 r

‐61.7 ± 2.0 g (FeF3)2

11B3u(D2h) 11B3u (D2h) ‐389.0 g

(FeCl3)2 11B3u(D2h)

11B3u (D2h) (D2h) r ‐156.4 ± 2.0 r

‐156.5 ± 2.0 g FeCO

5(C∞v)

5A2 (C2v)

3(C∞v)ggg [5(C∞v) or

3(C∞v)ww,

3(C∞v) hhh]

63.9 ± 3.5 iii

[65.9 ± 3.0] jjj Fe(CO)2

3g (D∞h) 3B1g (D2h)

3g‐ (D∞h)

kkk, [3g‐ (D∞h)

ww, hhh] 0.2 ± 4.9 iii [5.8 ± 2.0] jjj Fe(CO)3 (C3v)

3A' (Cs) [3A 2(C3v)hhh] ‐55.8 ± 7.6 iii

[‐53.4 ± 3.0] jjj Fe(CO)4

3B1 (C2v) 3B1 (C2v) [3B 2(C2v)

hhh] ‐105.1 ± 3.4 r ‐104.5 ± 2.8 iii [‐111.0 ± 4.0] jjj Fe(CO)5 (D3h) (D3h)

r, [1A1' (D3h)hhh] ‐174.0 ± 1.7 r

‐173.0 ± 1.6 p ‐173.0 ± 2.0 lll,g Fe(C5H5)

6A' (Cs) 6A' (Cs) 88.0 ± 3.8 p

Fe(C5H5)2 1A1g (D5d) (D5h)

mmm [1A1'(D5h) nnn] 57.9 ± 0.6 p

Fe(CO)4H2 1A1 (C2v) ‐131.0 p

Fe(CO)4(CH2CH2) 1A1 (C2v) ‐129.1 ± 2.2 p

CoH (C∞v)

3B1 (C2v) 3( C∞v) e 106.6 ± 3.2 qqq

CoSi (C∞v) 2A2 (C2v) 145.4 ± 5.0 g

CoGe (C∞v) 2A2 (C2v) 136.4 ± 5.2 g

CoO 4(C∞v) 4A1 (C2v) [4( C∞v) e] 74.0 ± 5.1 g CoCl (C∞v)

3B1 (C2v) 3(C∞v) r, 3 50.3 ± 1.6 pp

46.1 ± 3.0 r

19


Exp. Hf (298 K) d

B3LYP a ROHF b Exp. [Theor.] c CoF2 (D∞h)

4Ag (D2h) (C2v) r, [4g

‐ (D∞h) l, 4g (D∞h)

ppp] ‐85.2 ± 3.0 r ‐87.5 g CoCl2 (D∞h)

4Ag (D2h) 4g

‐ or 4 (D∞h) r, [4g

‐ (D∞h) l, ‐22.6 ± 1.0 pp

4g (D∞h) ppp] ‐20.1 ± 1.1 g

‐22.4 ± 1.9 r CoBr2 (D∞h)

4Ag (D2h) [4g (D∞h) ppp] 0.5 ± 1.1 g

CoCl3 5A1 (C2v)

5A1 (C2v) (C3v) r ‐39.1 ± 2.5 r

(CoCl2)2 7B3u (D2h)

7Au (D2h) (D2h) r ‐76.8 ± 4.0 g

‐83.8 ± 7.0 r (CoBr2)2

7A1 (C2v) 7A1 (C2v) ‐37.5 ± 4.0 g

Co(CO)4 (C3v) 2A' (Cs) ‐134.3 ± 1.8 p

‐163.0 g Co(CO)4H

1A1 (C2v) ‐136.0 ± 0.5 p ‐136.0 g Co(CO)2H(PF3)2

1A' (Cs) ‐550.0 g

Co(CO)3HPF3 1A' (Cs) ‐352.0 g

Co(SiF3) (CO)4 1A1 (C3v)

‐456.0 g NiH (C∞v)

2A1 (C2v) 2C∞v) p 85.7 ± 2.6 g

94.4 ± 3.7 qqq NiSi 1(C∞v) 135.3 ± 5.0 g NiGe 1(C∞v) 124.3 ± 5.1 g NiO 3(C∞v) 3A2 (C2v) [3‐ ( C∞v)

e] 75.0 ± 5.0 g NiS 3(C∞v) 3A2 (C2v) [3‐C∞v) h] 85.4 ± 4.0 r 81.7 ± 5.0 g NiF (C∞v)

2B1 (C2v) 2( C∞v)

e 17.5 g NiCl (C∞v)

2B1 (C2v) 43.5 ± 1.0 r 41.7 ± 1.0 pp 42.6 g NiBr (C∞v)

2B1 (C2v) 44.9 ± 5.0 g NiF2

3g (D∞h) 3B1g (D2h) [3g

‐ (D∞h) l] ‐77.8 ± 1.1 g

NiCl2 3g (D∞h)

3B1g (D2h) 3g(D∞h)

r, [3g‐ (D∞h)

l] ‐17.7 ± 0.6 r ‐17.4 ± 1.0 pp ‐15.7 ± 2.1 g NiBr2

3 g (D∞h) 3B1g (D2h) 4.7 ± 3.0 g

Ni(OH)2 3Bg (C2h)

3Bg (C2h) ‐60.8 ± 3.0 g NiCO 1(C∞v) (C∞v) kkk 35.1 ± 5.8 iii Ni(CO)2

1A1 (C2v) ‐39.0 ± 2.5 iii Ni(CO)3 (D3h) ‐94.5 ± 1.1 iii ‐93.0 ± 2.0 p Ni(CO)4

1A1 (Td) (Td) r ‐144.0 ± 0.6 p

‐143.8 ± 2.5 r Ni(PF3)4

1A1 (Td) [(Td) rrr] ‐953.4 ± 2.4 p

‐983.0 g

20


Exp. Hf (298 K) d

B3LYP a ROHF b Exp. [Theor.] c CuH 1(C∞v) 1+C∞v) p 65.9 ± 2.0 g CuGe (C∞v)

2B1 (C2v) 2 122.8 ± 4.2 g

CuO (C∞v) 2B1 (C2v) X2(C∞v) r 73.2 ± 10 r

76.5 g CuS (C∞v)

2B1 (C2v) [2C∞v) h] 75.1 ± 5.0 g CuSe (C∞v)

2B1 (C2v) [2C∞v) h] 70.3 ± 12 g CuF 1(C∞v) X 1(C∞v) r ‐3.2 ± 2.0 g

1.1 ± 3.0 sss ‐3.0 ± 4.0 r CuCl 1(C∞v) 1(C∞v) r 21.8 ± 0.4 r 19.3 ± 2.0 g CuBr 1(C∞v) 28.8 ± 6.0 g CuF2 (D∞h)

2Ag (D2h) 2g

+ (D∞h) r, [2g (D∞h)

l] ‐66.0 g ‐63.8 ± 3.0 r CuCl2 (D∞h)

2Ag (D2h) 2g (D∞h)

kkk, [2g (D∞h) l] ‐9.0 l

(CuCl)3 1A1 (C3v) (D3h)

r ‐61.8 ± 0.5 r ‐61.2 ± 1.0 g (CuBr)3 (D3h) ‐35.8 ± 2.1 g CuOH 1A' (Cs) 1A' (Cs)

kkk 28.0 ± 4.0 g ZnH 2(C∞v) 2A1 (C2v)

2+C∞v) p 62.9 ± 0.5 g ZnO 1(C∞v) 55.2 ± 1.0 ttt

52.8 ± 0.9 g ZnS 1(C∞v) 62.9 ± 1.0 ttt 48.7 ± 3.0 g ZnSe 1(C∞v) 60.0 ± 1.4 ttt 52.0 ± 4.8 g ZnCl 2(C∞v) 2A1 (C2v) 6.5 ± 1.0 g ZnBr 2(C∞v) 2A1 (C2v) 24.3 ± 7.0 g ZnF2

1g (D∞h) [1g+(D∞h)

l] ‐118.9 ± 1.1 g ZnCl2

1g (D∞h) [1g+(D∞h)

l] ‐63.5 ± 0.4 g ZnBr2

1g (D∞h) ‐44.4 g ZnCH3

2A1 (C3v) 2A' (Cs) 45.5 ± 4.0 p

26.0 ± 2.5 g Zn(CH3)2

1A1 (D3) 12.6 ± 0.3 p 12.9 ± 2.0 g Zn(CH2CH3)2 1A' (Cs) 13.3 ± 2.0 g 14.0 ± 1.0 p Zn(CH2CH2CH3)2

1A (C2) ‐4.1 ± 5.5 p (ZnCl2)2

1Ag (D2h) ‐168.0 g (ZnBr2)2

1Ag (D2h) ‐120.3 ± 3.5 g

21

References: a The ground state determined by B3LYP/cc‐pVTZ with the symmetry group given in parenthesis. b The ground state in ROHF calculations with the symmetry group given in parenthesis. c The ground state determined by experiments or suggested from previous theoretical studies (in

square brackets). d Some theoretical predictions are also given in square brackets. e Harrison, J. F. Chem. Rev. 2000, 100, 679. f Gingerich, K. A. J. Chem. Phys. 1968, 49, 19. g Yungman, V. S. Thermal Constants of Substances Wiley, New York, 1999. h Wu, Z. J.; Wang, M. Y.; Su, Z. M. J. Comput. Chem. 2006, 28, 703. (Theoretical study) i Hildenbrand, D. L.; Lau, K. H. J. Chem. Phys. 1995, 102, 3769. j Jackson, P.; Gadd, G. E.; Mackey, D. W.; van der Wall, H.; Willet, G. D. J. Phys. Chem. A 1998, 102,

8941. (Theoretical study) k Redondo, P.; Barrientos, C.; Largo, A. J. Phys. Chem. A 2006, 110, 4057. (Theoretical study) l Wang, S. G.; Schwarz, W. H. E. . J. Chem. Phys.1998, 109, 7252. (Theoretical study) m Russo, T. V.; Martin, R. L.; Hay, P. J. J. Chem. Phys. 1995, 102, 8023. (Theoretical study) n Zhang, Y.; Zhao, J.; Tang, G.; Zhu, L. Spectrochimica Acta Part A 2005, 62, 1. (Theoretical study) o Kordis, J.; Gingerich, K. A. J. Chem. Phys. 1977, 66, 483. p Mallard, W. G.; Linstrom, P. J. NIST Chemsitry WebBook; NIST Standard Reference Database Number

69; National Institute of Standards and Technology: Gaitherburg, MD, 2000. q Chen, Y.‐M.; Clemmer, D. E.; Armentrout, P. B. J. Chem. Phys. 1991, 95, 1228. r Chase, J. M. W.; Davies, C. A.; Downey, J. J. R.; Frurip, D. J.; McDonald, R. A.; Syverud, A. N. NIST‐

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Table S4. The ground states and experimental values (kcal mol‐1) of Hf (298 K) for 3d transition metal dimers in the test set.

Molecule Ground State a Exp.Hf (298 K) Sc2 Σ 154.2 ± 5.3 b, 142.2 ± 5.0 a,c Ti2 3g 195.0 ± 4.5 b, 194.9 ± 4.1 c, 189.5 ± 4.2 a V2 Σ 181.2 ± 4.0 a, 187.4 ± 5.2 b, 187.8 ± 5.0 c Cr2 Σ 156.2 ± 0.9 d, 153.0 ± 7.1 b, 153.0 ± 5.0 c, 155.9 ± 3.0 a, 153.9 ± 1.4 e Mn2

11u ( Σ ) 127.5 ± 6.1 b 124.8 ± 6.9 c 116.4 a Fe2 7u 171.0 ± 2.1 a 178.3 ± 8.0 b 173.6 ± 5.0 c Co2 5g 164.2 ± 6.0 a 164.0 ± 6.3 b 163.2 ± 6.0 c Ni2 Σ 156.9 ± 4.0 a 148.0 ± 5.0 b 149.6 ± 5.0 c Cu2 Σ 115.3 ± 1.3 c 114.4 ± 1.8 a 113.8 ± 2.6 b Zn2 Σ 60.7 a 57.7 ± 1.5 b 57.6 ± 1.5 c CrCu 6 138.1 ± 6.0 b CoCu 33) f 143.5 ± 5.1 b NiCu 2 133.4 ± 5.0 b References: a Homonuclear dimers: Gustev, G. L.; Bauschlicher, Jr.; C. W. J. Phys. Chem. A 2003, 107, 4755 and references therein. Mixed dimers: Gustev, G. L.; Monchena, M. D.; Bauschlicher, Jr.; C. W. Patridge III, H. J. Chem. Phys. 2004, 121, 6785. The uncertainty of dissociation energy D0 is used for Fe2 and Co2,

and the sum of the uncertainty of atomic Hf (298 K) is applied to V2 and Ni2. b Yungman, V. S. Thermal Constants of Substances Wiley, New York, 1999. c Ginerich, K. A. Faraday Symp. Chem. Soc. 1980, 14, 109. d Hilpert, K.; Ruthardt, K. Ber. Bunsen‐Ges. (Phys. Chem.) 1987, 91, 724. (German journal) e Simard, B.; Lebeault‐Dorget, M.‐A.; Marijnissen A.; ter Meulen, J. J. J. Chem. Phys.1998, 108, 9668. f Predicted by B3LYP in this work.

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Table S5. Signed deviations in kcal mol‐1 of the ROHF‐ and UHF‐ccCA‐TM predicted Hf (298.15 K) with respect to experimental values (experimental value – theoretical predicted value) for the ccCA‐TM/11all set of 225 molecules.

Exp.: experimental values; Error: reported uncertainty; P: ROHF‐ccCA‐TM with the Peterson extrapolation for complete basis set limits (see Eq. 3 in text); S3: ROHF‐ccCA‐TM with inverse cubic power extrapolation for complete basis set limits (see Eq. 4 in text); S4: ROHF‐ccCA‐TM with inverse quartic power extrapolation complete basis set limits (see Eq. 5 in text); PS3: ROHF‐ccCA‐TM with the average of inverse cubic power (S3) and the Peterson extrapolation complete basis set limits; UP: UHF‐ccCA‐TM with the Peterson extrapolation complete basis set limits (see Eq. 3 in text).

Molecule Exp. Error P S4 S3 PS3 UP ScH 93.7 ‐ 6.0 6.0 6.1 6.1 5.7 ScN 91.0 20.0 ‐27.9 ‐28.0 ‐27.4 ‐27.6 ‐28.2 ScO ‐13.0 2.2 ‐5.9 ‐6.0 ‐5.7 ‐5.8 ‐6.2 ScS 41.7 3.1 ‐3.4 ‐3.6 ‐3.1 ‐3.3 ‐3.6 ScSe 53.0 4.1 4.2 4.0 4.5 4.3 3.9 ScF ‐33.9 3.4 ‐0.7 ‐0.8 ‐0.7 ‐0.7 ‐1.0 ScB2 150.6 21.0 ‐50.7 ‐50.7 ‐50.3 ‐50.5 ScC2 152.7 4.0 ‐2.7 ‐2.8 ‐2.1 ‐2.4 ‐2.8 ScF2 ‐157.4 7.0 0.8 0.7 1.0 0.9 ‐18.8 ScF3 ‐300.4 3.6 ‐3.3 ‐3.5 ‐3.0 ‐3.2 ‐3.3 ScCl3 ‐160.5 2.1 4.4 4.2 5.0 4.7 4.8 ScBr3 ‐109.3 2.6 17.8 17.5 18.3 18.0 18.0 ScC4 196.2 5.0 0.3 0.3 1.5 0.9 ‐14.3 Sc2O ‐4.5 11.0 ‐19.1 ‐19.2 ‐18.8 ‐19.0 ‐19.6 (ScCl3)2 ‐369.0 8.0 13.1 12.6 14.1 13.6 13.7 Sc(C5H5)3 20.0 1.4 ‐0.3 0.0 5.4 2.5 1.2

26

Molecule Exp. Error P S4 S3 PS3 UP TiH 116.4 2.3 2.8 2.8 2.9 2.8 6.7 TiB 181.3 15.0 ‐28.0 ‐28.0 ‐27.9 ‐28.0 TiC 169.8 ‐ ‐28.6 ‐28.7 ‐28.3 ‐28.4 ‐29.3 TiN 112.0 7.0 ‐1.2 ‐1.4 ‐0.8 ‐1.0 5.3 TiO 13.7 2.2 ‐2.5 ‐2.6 ‐2.2 ‐2.3 ‐3.5 TiS 76.2 2.2 3.3 3.2 3.7 3.5 0.6 TiSe 76.8 10.0 ‐0.9 ‐1.0 ‐0.5 ‐0.7 ‐3.0 TiF ‐4.0 8.0 ‐9.7 ‐9.7 ‐9.5 ‐9.6 ‐9.6 TiCl 40.9 2.0 ‐4.5 ‐4.6 ‐4.4 ‐4.4 3.6 TiBr 50.8 10.0 ‐6.7 ‐6.8 ‐6.5 ‐6.6 ‐13.7 TiC2 175.4 3.0 ‐12.1 ‐12.1 ‐11.4 ‐11.8 ‐13.1 TiO2 ‐73.0 3.0 ‐5.1 ‐5.3 ‐4.5 ‐4.8 ‐5.7 TiF2 ‐164.5 10.0 ‐31.5 ‐31.6 ‐31.1 ‐31.3 ‐30.2 TiCl2 ‐49.0 2.0 ‐0.6 ‐0.7 ‐0.2 ‐0.4 ‐0.8 TiBr2 ‐42.8 5.0 ‐19.8 ‐19.9 ‐19.4 ‐19.6 ‐19.7 TiF3 ‐284.0 10.0 ‐18.4 ‐18.6 ‐17.9 ‐18.2 ‐23.7 TiCl3 ‐121.5 2.0 1.9 1.6 2.4 2.1 1.6 TiBr3 ‐89.6 2.5 ‐4.4 ‐4.7 ‐4.0 ‐4.2 ‐4.5 TiC4 217.9 0.5 ‐6.2 ‐6.3 ‐5.0 ‐5.6 ‐6.2 TiF4 ‐370.8 5.0 3.1 2.8 3.6 3.3 2.7 TiCl4 ‐182.4 0.7 2.0 1.6 2.6 2.3 2.1 TiBr4 ‐131.0 0.2 3.9 3.4 4.3 4.1 3.8 TiOF ‐103.5 ‐ ‐10.7 ‐10.8 ‐10.2 ‐10.4 ‐2.9 TiOCl ‐58.4 ‐ ‐1.6 ‐1.8 ‐1.1 ‐1.4 3.5 TiOF2 ‐221.1 ‐ 11.1 10.9 11.7 11.4 10.7 TiOCl2 ‐130.4 ‐ 12.8 12.4 13.3 13.0 12.5 TiCl3Br ‐169.8 ‐ 2.4 2.1 3.0 2.7 2.5 TiCl2Br2 ‐157.2 ‐ 2.5 2.1 3.0 2.8 2.5 TiClBr3 ‐144.6 ‐ 2.7 2.3 3.2 2.9 2.7 (TiCl3)2 ‐301.0 ‐ ‐7.4 ‐7.8 ‐6.2 ‐6.8 ‐7.5 Ti(C5H5)Cl3 ‐124.5 1.6 13.7 13.5 16.0 14.9 14.2

27

Molecule Exp. Error P S4 S3 PS3 UP VH 124.9 1.6 3.7 3.7 3.7 3.7 3.6 VC 181.6 15.0 ‐24.3 ‐24.4 ‐23.9 ‐24.1 ‐27.2 VN 121.0 3.0 ‐2.9 ‐3.1 ‐2.5 ‐2.7 ‐8.7 VO 31.8 2.0 ‐1.0 ‐1.1 ‐0.6 ‐0.8 ‐6.2 VS 80.4 3.2 ‐7.4 ‐7.5 ‐7.1 ‐7.3 ‐10.0 VSe 96.2 ‐ 5.0 4.9 5.3 5.1 2.6 VF 0.7 15.0 ‐13.7 ‐13.8 ‐13.6 ‐13.6 ‐14.0 VCl 49.7 2.0 ‐5.9 ‐6.0 ‐5.7 ‐5.8 ‐5.9 VBr 46.2 10.0 ‐21.0 ‐21.1 ‐20.9 ‐21.0 ‐21.0 VC2 184.1 5.0 ‐12.0 ‐12.1 ‐11.4 ‐11.7 ‐12.5 VO2 ‐41.6 3.3 ‐1.8 ‐2.1 ‐1.2 ‐1.5 ‐11.3 VCl2 ‐34.8 2.0 ‐3.5 ‐3.6 ‐3.1 ‐3.3 VBr2 ‐36.5 ‐ ‐29.5 ‐29.7 ‐29.2 ‐29.4 ‐30.7 VCl3 ‐85.6 2.0 ‐1.8 ‐2.0 ‐1.3 ‐1.5 ‐3.2 VBr3 ‐61.6 ‐ ‐16.6 ‐16.8 ‐16.1 ‐16.3 ‐13.1 VC4 232.4 5.0 ‐9.6 ‐9.6 ‐8.3 ‐9.0 ‐9.6 VCl4 ‐126.1 0.6 0.5 0.1 1.0 0.7 0.4 VBr4 ‐84.0 ‐ ‐4.3 ‐4.7 ‐3.8 ‐4.1 ‐3.8 VF5 ‐343.2 0.2 2.3 1.9 2.9 2.6 2.0 VOCl3 ‐166.4 1.3 ‐8.0 ‐8.4 ‐7.4 ‐7.7 ‐8.0 VO(OH)3 ‐250.0 ‐ 4.5 4.2 5.8 5.2 4.1 VBrCl3 ‐119.4 ‐ ‐3.9 ‐4.3 ‐3.4 ‐3.6 ‐5.8 V4O10 ‐675.0 5.0 ‐3.3 ‐4.4 ‐0.7 ‐2.0 ‐5.4

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Molecule Exp. Error P S4 S3 PS3 UP CrH 101.7 1.6 5.8 5.8 5.9 5.9 6.1 CrGe 144.1 7.1 ‐10.9 ‐10.9 ‐10.7 ‐10.8 ‐7.3 CrN 120.7 5.0 1.8 1.7 2.2 2.0 ‐3.7 CrO 43.6 1.6 ‐0.7 ‐0.7 ‐0.3 ‐0.5 ‐5.7 CrS 78.4 5.1 ‐4.2 ‐4.3 ‐3.8 ‐4.0 7.4 CrF 4.6 2.4 7.4 7.3 7.6 7.5 7.6 CrCl 33.7 1.6 ‐0.9 ‐0.9 ‐0.7 ‐0.8 ‐0.7 CrBr 44.6 6.0 ‐14.0 ‐14.1 ‐13.8 ‐13.9 11.2 CrC2 186.4 5.0 ‐3.3 ‐3.3 ‐2.6 ‐3.0 CrO2 ‐23.7 1.2 ‐1.4 ‐1.6 ‐0.8 ‐1.1 ‐4.7 CrF2 ‐103.2 3.0 3.8 3.7 4.2 4.0 4.0 CrCl2 ‐28.1 0.4 3.2 3.1 3.6 3.4 3.4 CrBr2 ‐14.1 4.3 ‐5.3 ‐5.5 ‐5.0 ‐5.2 10.8 CrO3 ‐77.3 1.0 ‐8.0 ‐8.2 ‐7.1 ‐7.6 ‐8.0 CrF3 ‐199.8 3.4 ‐3.5 ‐3.6 ‐2.9 ‐3.2 ‐3.4 CrCl3 ‐67.6 1.5 3.5 3.2 4.0 3.7 3.2 CrCl4 ‐94.8 3.3 5.8 5.4 6.3 6.1 CrBr4 ‐51.3 4.5 5.2 4.8 5.7 5.5 CrOH 18.9 1.8 4.8 4.8 5.2 5.0 2.9 CrOF ‐73.3 1.9 ‐2.3 ‐2.4 ‐1.7 ‐2.0 CrOF2 ‐153.3 3.4 ‐6.1 ‐6.4 ‐5.4 ‐5.8 ‐6.1 CrOCl2 ‐80.4 5.4 ‐12.9 ‐13.2 ‐12.3 ‐12.6 ‐12.7 CrO2Cl ‐74.2 5.2 7.8 7.5 8.4 8.1 7.4 CrClFO2 ‐161.2 1.1 0.7 1.7 1.4 1.3 CrO2F2 ‐201.6 5.0 0.0 ‐0.4 0.6 0.3 0.1 CrO2Cl2 ‐124.1 1.0 ‐1.0 ‐1.5 ‐0.4 ‐0.7 ‐0.7 Cr(OH)2 ‐76.8 1.2 0.1 0.1 1.0 0.6 0.6 CrO2(OH)2 ‐181.6 1.7 1.3 1.0 2.5 1.9 1.4 (CrCl2)2 ‐116.9 8.0 ‐11.6 ‐11.9 ‐10.8 ‐11.2 ‐12.9 (CrBr2)2 ‐79.8 8.0 ‐18.8 ‐19.2 ‐18.1 ‐18.5 ‐20.8 (CrO3)3 ‐389.0 10.0 ‐6.8 ‐7.8 ‐4.7 ‐5.8 ‐7.9 Cr(CO)3 ‐44.0 10.0 ‐5.0 ‐5.2 ‐3.2 ‐4.1 ‐4.7 Cr(CO)4 ‐102.0 6.0 1.4 1.1 3.6 2.5 1.9 Cr(CO)5 ‐153.9 3.1 14.7 14.3 17.3 16.0 15.4 Cr(CO)6 ‐240.0 1.1 ‐2.2 ‐2.7 0.7 ‐0.7 ‐1.3

29

Molecule Exp. Error P S4 S3 PS3 UP MnH 87.3 4.6 4.2 4.3 4.3 4.3 4.3 MnO 29.6 3.0 ‐9.5 ‐9.6 ‐9.1 ‐9.3 ‐15.6 MnS 63.3 2.0 ‐4.1 ‐4.2 ‐3.8 ‐3.9 ‐7.6 MnSe 73.0 4.0 6.0 5.9 6.3 6.1 3.1 MnF ‐19.9 3.0 ‐0.5 ‐0.5 ‐0.3 ‐0.4 ‐0.3 MnCl 15.8 1.6 ‐0.2 ‐0.3 ‐0.1 ‐0.2 ‐0.1 MnBr 20.1 ‐6.8 ‐6.9 ‐6.7 ‐6.8 ‐6.6 MnF2 ‐126.2 1.0 4.0 3.9 4.4 4.2 4.2 MnCl2 ‐62.6 1.0 ‐2.3 ‐2.5 ‐1.9 ‐2.1 ‐3.0 MnBr2 ‐41.9 3.0 ‐3.4 ‐3.6 ‐3.1 ‐3.2 ‐3.1 MnF3 ‐188.0 14.0 ‐6.1 ‐6.2 ‐5.5 ‐5.8 ‐5.8 MnF4 ‐231.0 17.0 ‐15.8 ‐16.1 ‐15.2 ‐15.5 MnOH 3.3 3.2 3.7 3.7 4.1 3.9 3.9 (MnCl2)2 ‐168.2 4.0 ‐12.8 ‐13.2 ‐12.1 ‐12.5 ‐12.1 (MnBr2)2 ‐123.9 6.0 ‐12.7 ‐13.2 ‐12.1 ‐12.4 ‐12.0 Mn(CO)5 ‐179.4 1.2 ‐11.1 ‐11.6 ‐8.4 ‐9.8 ‐11.2 Mn(CO)5H ‐176.8 2.2 10.0 9.5 12.7 11.3 10.6 Mn(CO)5Cl ‐219.5 3.1 ‐2.1 ‐2.7 0.6 ‐0.8 ‐1.2 Mn(CO)5Br ‐210.9 2.2 ‐0.7 ‐1.3 2.0 0.6 0.1 Mn(CO)3 (C5H5) ‐102.0 0.7 ‐3.3 ‐3.5 0.4 ‐1.5 ‐2.4

30

Molecule Exp. Error P S4 S3 PS3 UP FeH 113.9 1.9 4.7 4.7 5.0 4.9 ‐0.1 FeO 61.1 3.0 ‐1.8 ‐1.9 ‐1.5 ‐1.7 ‐9.0 FeS 88.6 3.9 ‐4.2 ‐4.3 ‐3.8 ‐4.0 ‐7.2 FeF 11.4 5.0 1.5 1.5 1.7 1.6 ‐10.2 FeCl 49.5 1.6 1.7 1.7 1.9 1.8 ‐5.2 FeBr 69.1 20.0 9.9 9.7 10.0 9.9 4.3 FeF2 ‐93.1 3.4 12.2 12.1 12.6 12.4 ‐2.3 FeCl2 ‐32.8 1.0 ‐0.3 ‐0.5 0.0 ‐0.1 ‐7.0 FeBr2 ‐9.9 0.5 ‐0.1 ‐0.4 0.2 0.0 ‐5.2 FeF3 ‐178.2 ‐ ‐7.9 ‐8.1 ‐7.6 ‐7.8 ‐7.8 FeCl3 ‐60.6 1.0 ‐1.5 ‐1.8 ‐1.2 ‐1.3 ‐1.5 FeBr3 ‐30.0 1.0 ‐3.1 ‐3.4 ‐2.9 ‐3.0 ‐2.9 Fe(OH)2 ‐79.0 0.5 ‐9.3 ‐9.5 ‐8.5 ‐8.9 ‐18.4 (FeCl2)2 ‐103.1 1.0 ‐0.2 ‐0.6 0.7 0.2 (FeBr2)2 ‐60.5 1.9 ‐6.6 ‐7.1 ‐5.8 ‐6.2 (FeF3)2 ‐389.0 ‐ ‐0.5 ‐0.8 0.0 ‐0.2 (FeCl3)2 ‐156.4 2.0 ‐0.8 ‐1.4 ‐0.3 ‐0.5 ‐0.4 FeCO 63.9 3.5 ‐7.9 ‐8.0 ‐7.3 ‐7.6 ‐11.4 Fe(CO)2 0.2 4.9 ‐8.5 ‐8.7 ‐7.3 ‐7.9 ‐14.1 Fe(CO)3 ‐55.8 7.6 ‐6.9 ‐7.2 ‐5.2 ‐6.0 ‐16.4 Fe(CO)4 ‐105.1 3.4 6.3 5.9 8.4 7.4 2.3 Fe(CO)5 ‐174.0 1.7 5.1 4.6 7.7 6.4 5.6 Fe(C5H5) 88.0 3.8 ‐18.3 ‐18.3 ‐16.4 ‐17.4 ‐17.8 Fe(C5H5)2 57.9 0.6 2.2 2.2 6.2 4.2 2.8 Fe(CO)4H2 ‐131.0 ‐ 7.1 6.7 9.3 8.2 7.3 Fe(CO)4(CH2CH2) ‐129.1 2.2 3.4 3.1 6.4 4.9 3.9

31

Molecule Exp. Error P S4 S3 PS3 UP CoH 106.6 3.2 2.6 2.6 2.9 2.8 ‐8.6 CoSi 145.4 5.0 ‐3.9 ‐4.1 ‐3.5 ‐3.7 CoGe 136.4 5.2 ‐3.2 ‐3.4 ‐2.9 ‐3.0 12.3 CoO 74.0 5.1 2.5 2.5 2.9 2.7 2.4 CoCl 50.3 1.6 ‐6.4 ‐6.5 ‐6.0 ‐6.2 ‐9.6 CoF2 ‐85.2 3.0 0.8 0.7 1.1 1.0 0.9 CoCl2 ‐22.6 1.0 ‐1.7 ‐1.9 ‐1.3 ‐1.5 5.7 CoBr2 0.5 1.1 0.1 ‐0.1 0.4 0.2 ‐0.8 CoCl3 ‐39.1 2.5 ‐4.6 ‐5.0 ‐4.3 ‐4.5 ‐5.0 (CoCl2)2 ‐76.8 4.0 ‐21.9 ‐22.3 ‐21.0 ‐21.4 (CoBr2)2 ‐37.5 4.0 ‐23.2 ‐23.7 ‐22.4 ‐22.8 ‐26.7 Co(CO)4 ‐134.3 1.8 ‐10.1 ‐10.5 ‐8.1 ‐9.1 ‐10.8 Co(CO)4H ‐136.0 0.5 0.5 0.0 2.6 1.5 0.5 Co(CO)2H(PF3)2 ‐550.0 ‐ ‐2.1 ‐2.8 0.6 ‐0.8 ‐1.9 Co(CO)3H(PF3) ‐352.0 ‐ ‐11.8 ‐12.3 ‐9.4 ‐10.6 ‐11.6 Co(SiF3)(CO)4 ‐456.0 ‐ ‐22.3 ‐22.9 ‐19.5 ‐20.9 ‐21.8 NiH 85.7 2.6 ‐4.0 ‐4.0 ‐3.7 ‐3.8 NiSi 135.3 5.0 ‐0.3 ‐0.5 0.1 ‐0.1 ‐0.8 NiGe 124.3 5.1 ‐0.8 ‐1.0 ‐0.5 ‐0.7 ‐1.5 NiO 75.0 5.0 4.5 4.4 4.8 4.7 3.7 NiS 85.4 4.0 ‐6.9 ‐7.0 ‐6.5 ‐6.7 ‐3.9 NiF 17.5 ‐ ‐3.3 ‐3.4 ‐2.9 ‐3.1 ‐21.1 NiCl 43.5 1.0 ‐1.2 ‐1.3 ‐0.8 ‐1.0 ‐1.5 NiBr 44.9 5.0 ‐8.5 ‐8.7 ‐8.2 ‐8.4 ‐8.4 NiF2 ‐77.8 1.1 1.5 1.3 1.8 1.7 1.4 NiCl2 ‐17.7 0.6 ‐3.6 ‐3.8 ‐3.3 ‐3.4 ‐3.7 NiBr2 4.7 3.0 ‐5.9 ‐6.2 ‐5.6 ‐5.8 Ni(OH)2 ‐60.8 3.0 ‐7.0 ‐7.1 ‐6.2 ‐6.6 ‐7.1 Ni(CO) 35.1 5.8 ‐2.9 ‐3.1 ‐2.2 ‐2.6 ‐3.4 Ni(CO)2 ‐39.0 2.5 ‐9.4 ‐9.7 ‐8.2 ‐8.8 ‐9.7 Ni(CO)3 ‐94.5 1.1 ‐5.5 ‐5.9 ‐4.0 ‐4.8 ‐5.7 Ni(CO)4 ‐144.0 0.6 ‐0.6 ‐1.2 1.3 0.3 ‐0.6 Ni(PF3)4 ‐953.4 2.4 3.6 2.5 6.7 5.1 4.1

32

Molecule Exp. Error P S4 S3 PS3 UP CuH 65.9 2.0 ‐2.3 ‐2.3 ‐2.2 ‐2.3 ‐2.3 CuGe 122.8 4.2 2.1 2.1 2.3 2.2 2.1 CuO 73.2 10.0 ‐0.5 ‐0.6 ‐0.3 ‐0.4 CuS 75.1 5.0 ‐4.5 ‐4.6 ‐4.3 ‐4.4 ‐9.9 CuSe 70.3 12.0 ‐2.5 ‐2.6 ‐2.3 ‐2.4 ‐8.6 CuF 1.1 3.0 0.8 0.7 1.0 0.9 0.9 CuCl 21.8 0.4 0.0 ‐0.1 0.2 0.1 0.3 CuBr 28.8 6.0 ‐0.7 ‐0.9 ‐0.6 ‐0.6 ‐0.5 CuF2 ‐66.0 ‐ 1.3 1.2 1.5 1.4 ‐4.1 CuCl2 ‐9.0 ‐ ‐7.3 ‐7.5 ‐7.1 ‐7.2 ‐5.9 (CuCl)3 ‐61.8 0.5 4.8 4.4 5.4 5.1 5.6 (CuBr)3 ‐35.8 2.1 5.2 4.7 5.8 5.5 5.9 CuOH 28.0 4.0 14.6 14.6 15.0 14.8 14.7 ZnH 62.9 0.5 ‐0.3 ‐0.3 ‐0.2 ‐0.3 ‐0.2 ZnO 52.8 0.9 0.0 ‐0.1 0.3 0.1 0.0 ZnS 62.9 1.0 ‐0.9 ‐1.0 ‐0.6 ‐0.7 ‐0.6 ZnSe 60.0 1.4 0.5 0.4 0.7 0.6 0.7 ZnCl 6.5 1.0 ‐5.1 ‐5.2 ‐4.9 ‐5.0 ‐5.1 ZnBr 24.3 7.0 3.5 3.4 3.7 3.6 3.7 ZnF2 ‐118.9 1.1 2.6 2.5 2.9 2.7 2.7 ZnCl2 ‐63.5 0.4 ‐1.0 ‐1.2 ‐0.7 ‐0.8 ‐0.6 ZnBr2 ‐44.4 ‐ ‐1.0 ‐1.2 ‐0.7 ‐0.8 ‐0.7 ZnCH3 45.5 4.0 ‐6.2 ‐6.1 ‐5.7 ‐5.9 ‐6.0 Zn(CH3)2 12.6 0.3 0.8 0.9 1.9 1.3 1.0 Zn(CH2CH3)2 13.3 2.0 1.0 1.1 2.9 2.0 1.5 Zn(CH2CH2CH3)2 ‐4.1 5.5 ‐5.2 ‐4.9 ‐2.4 ‐3.8 ‐4.5 (ZnCl2)2 ‐168.0 ‐ ‐20.5 ‐21.0 ‐19.9 ‐20.2 ‐19.7 (ZnBr2)2 ‐120.3 3.5 ‐12.3 ‐12.9 ‐11.8 ‐12.1 ‐11.7

33

Molecule Exp. Error P S4 S3 PS3 UP Sc2 154.2 5.3 ‐16.6 ‐16.7 ‐16.6 ‐16.6 ‐35.2 Ti2 195.0 4.5 ‐6.7 ‐6.8 ‐6.3 ‐6.5 ‐ V2 181.2 4.0 ‐29.1 ‐29.4 ‐28.8 ‐29.0 ‐15.7 Cr2 156.2 2.0 ‐10.6 ‐11.0 ‐10.3 ‐10.5 ‐11.1 Mn2 127.5 6.1 ‐27.1 ‐27.2 ‐26.8 ‐27.0 ‐31.7 Fe2 171.0 2.1 ‐47.8 ‐47.9 ‐47.2 ‐47.5 ‐38.1 Co2 164.2 6.0 ‐28.1 ‐28.2 ‐27.5 ‐27.8 ‐47.2 Ni2 156.9 4.0 ‐11.1 ‐11.3 ‐10.7 ‐10.9 ‐7.9 Cu2 115.3 1.3 3.4 3.3 3.4 3.4 3.5 Zn2 60.7 ‐ ‐0.4 ‐0.4 ‐0.4 ‐0.4 ‐0.4 CrCu 138.1 6.0 0.4 0.3 0.4 0.4 ‐0.8 CoCu 143.5 5.1 ‐7.9 ‐8.0 ‐7.7 ‐7.8 ‐14.2 NiCu 133.4 5.0 ‐2.5 ‐2.7 ‐2.3 ‐2.4 ‐6.5

34

Table S6. Listing of 42 molecules meeting the requirement of diagnostics: C02 > 0.90, T1 < 0.05, and D1 <

0.10 for reliable single reference calculations.

ScO CrF2 FeF Cu2 ScS CrCl2 FeCl CuCo ScF MnH FeBr ZnH ScF2 MnF FeF2 ZnS TiO MnCl FeCl2 ZnSe TiF MnBr FeBr2 ZnCl TiF2 MnF2 CoF2 ZnBr TiCl2 MnCl2 CoCl2 ZnF2 TiBr2 MnBr2 CoBr2 ZnCl2 VCl2 MnOH NiF2 ZnBr2 VBr2 Zn2

35

(a)

(b)

0

0.05

0.1

0.15

0.2

‐15 ‐10 ‐5 0 5 10 15

T 1

ccCA‐TM deviation (kcal mol‐1)

0

0.1

0.2

0.3

0.4

‐15 ‐10 ‐5 0 5 10 15

D1


36

(c)

Figure S1. Scatter plot of (a) T1 diagnostics; (b) D1 diagnostics; (c) spin contamination (<S2‐Sz2‐Sz>, open

shell molecules only) against the signed deviations of ccCA‐TM predictions from experimental enthalpies of formation for test set with experimental error ≤ 1.0 kcal mol‐1. All diagnostics results are extracted from the CCSD(T)/cc‐pVTZ‐DK calculation.

0

0.2

0.4

0.6

0.8

1‐15 ‐10 ‐5 0 5 10 15

Spin contamination


37

(a)

(b)

0

0.05

0.1

0.15

0.2

‐15 ‐10 ‐5 0 5 10 15

T 1


0

0.1

0.2

0.3

0.4

‐15 ‐10 ‐5 0 5 10 15

D1


38

(c)



0

0.2

0.4

0.6

0.8

1‐15 ‐10 ‐5 0 5 10 15

Spin contamination


39

(a)

(b)

0

0.05

0.1

0.15

0.2

‐15 ‐10 ‐5 0 5 10 15

T 1


0

0.1

0.2

0.3

0.4

‐15 ‐10 ‐5 0 5 10 15

D1


40

(c)



0

0.2

0.4

0.6

0.8

1‐15 ‐10 ‐5 0 5 10 15

Spin contamination


41

(a)

(b)

0

0.05

0.1

0.15

0.2

‐15 ‐10 ‐5 0 5 10 15

T 1


0

0.1

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‐15 ‐10 ‐5 0 5 10 15

D1


42

(c)



0

0.2

0.4

0.6

0.8

1‐15 ‐10 ‐5 0 5 10 15

Spin contamination


43

(a)

(b)

0

0.05

0.1

0.15

0.2

‐15 ‐10 ‐5 0 5 10 15

T 1


0

0.1

0.2

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0.4

‐15 ‐10 ‐5 0 5 10 15

D1


44

(c)



0

0.2

0.4

0.6

0.8

1‐15 ‐10 ‐5 0 5 10 15

Spin contamination


Towards Accurate Thermochemistry of First Row Transition ... · Table S1. Atomic ROHF‐ccCA‐TM...

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