Supporting Information: Multireference Protonation Energetics of a Dimeric
Model of Nitrogenase Iron–Sulfur Clusters
Huanchen Zhai,
1,
a)
Seunghoon Lee,
1
Zhi-Hao Cui,
1
Lili Cao,
2
Ulf Ryde,
2,
b)
and Garnet Kin-Lic Chan
1,
c)
1)
Division of Chemistry and Chemical Engineering, California Institute of Technology, Pasadena, CA 91125,
USA
2)
Department of Theoretical Chemistry, Lund University, P. O. Box 124, SE-221 00 Lund,
Sweden
(Dated: 31 October 2023)
I. CLUSTER GEOMETRIES
Cluster geometries are given in XYZ coordinates with the unit Angstrom.
A. Optimized with def2-SV(P)/UKS-TPSS/DFTD3
27
HC, Energy = -4717.139080700 H
C -1.0654597 -1.6165964 -3.6938910
H -1.4383635 -0.5689779 -3.6741341
H -1.7807115 -2.2443224 -3.1121367
H -1.0773907 -1.9924332 -4.7494055
S 0.6243829 -1.6537410 -2.9602556
C 0.4156598 1.7876147 -4.0556776
H 1.3488982 2.3835358 -3.9218054
H -0.1330190 2.2251636 -4.9293434
H 0.7135941 0.7422418 -4.2919146
S -0.6070437 1.7896179 -2.5222937
C -0.8232495 2.8573739 1.4681234
H -0.0877151 2.8066116 0.6407689
H -0.9439809 3.9246222 1.7897946
H -1.7975667 2.5226444 1.0498580
S -0.2735647 1.7807874 2.8579066
C -1.0643237 -1.5242334 4.0337374
H -1.0304628 -1.8368555 5.1103107
H -1.8734238 -2.1231958 3.5494502
H -1.3541746 -0.4526895 3.9781077
S 0.5588840 -1.7538671 3.1864833
Fe 0.4943827 0.0464709 -1.2052434
Fe 0.5810012 -0.0475200 1.4684925
S 2.2702018 0.5987571 0.0818694
C -0.9804810 -0.8504359 0.1595883
H -0.9278775 -1.9603768 0.2106940
H -1.5301625 -0.5677658 -0.7796813
H -1.6330329 -0.4914309 0.9945982
Listing S1. HC
27
HS, Energy = -4717.096074143 H
C -1.4481492 -1.2918793 -4.0685921
H -1.5592125 -0.1859823 -4.0893224
H -2.3309980 -1.7079134 -3.5297987
H -1.4760151 -1.6885040 -5.1175674
S 0.1243831 -1.7171690 -3.2045707
C 1.0341701 1.7983129 -3.6269368
a)
Electronic mail: hczhai.ok@gmail.com
b)
Electronic mail: ulf.ryde@compchem.lu.se
c)
Electronic mail: gkc1000@gmail.com
S2
H 1.9627435 1.9656559 -3.0387507
H 0.9926332 2.5651117 -4.4445661
H 1.1042400 0.7824705 -4.0723829
S -0.4446417 1.8649325 -2.5294114
C -1.1427404 2.6271747 1.3777265
H -0.7051544 2.6282955 0.3581567
H -1.2853067 3.6896251 1.7066593
H -2.1508112 2.1651199 1.2944240
S -0.0778785 1.6928495 2.5587062
C -0.7929520 -1.4324890 4.2467679
H -0.9625390 -0.3357608 4.1885620
H -0.5400427 -1.7119510 5.3045419
H -1.7588854 -1.9373028 4.0010839
S 0.5386887 -1.8989304 3.0569739
Fe -0.0624496 -0.2245743 -1.3014183
Fe 0.1805793 -0.3587873 1.2612831
S 2.1356417 0.1952062 -0.2457191
C -1.2915962 -0.9617811 0.0689167
H 1.9086364 1.5088483 0.0713138
H -2.2983991 -0.4932717 0.2239739
H -1.4219432 -2.0743068 0.0479475
Listing S2. HS
27
HFe , Energy = -4717.084045403 H
C -1.7030912 -0.2687576 -3.8857510
H -1.4276567 0.6161659 -3.2739484
H -2.7282115 -0.5817080 -3.5791673
H -1.7544034 0.0472283 -4.9585791
S -0.4654014 -1.5971491 -3.6068456
C 1.3427752 1.2911521 -3.6530591
H 2.4027725 1.5361646 -3.9146487
H 0.7051324 2.0932763 -4.0999022
H 1.0611069 0.3183708 -4.1168671
S 1.1257526 1.1531598 -1.8302475
C -0.5460690 2.6148722 1.2254132
H 0.3817785 2.2964072 1.7410684
H -0.7581861 3.6865849 1.4682270
H -0.3516724 2.5166490 0.1383690
S -1.9524226 1.5437145 1.7437219
C -1.2593992 -1.2001762 4.2059136
H -0.1794134 -1.4477025 4.1290192
H -1.6496014 -1.5773749 5.1869269
H -1.3493637 -0.0933792 4.1760396
S -2.1872294 -1.9182902 2.7849438
Fe 0.2293122 -1.0722584 -1.1389980
Fe -1.0895429 -0.6236298 1.1100321
S 1.1201274 -0.6801252 1.0718109
C -1.6833719 -1.3940353 -0.5791815
H 1.1279016 -2.5680078 -1.3656985
H -2.5031122 -0.8682227 -1.1171969
H -1.7445096 -2.4939284 -0.7433938
Listing S3. HFe
27
HFe2 , Energy = -4717.102540727 H
C -0.6004690 -1.8541396 -4.3931123
H -0.9885128 -0.8116508 -4.4441158
H -1.2233186 -2.5109691 -5.0545639
H 0.4332653 -1.8614472 -4.8208224
S -0.6420813 -2.4169491 -2.6407698
C 0.4911160 1.7119732 -3.4952934
H 1.1454118 1.7908560 -2.6017265
H 0.4940557 2.6834804 -4.0526033
H 0.9297739 0.9375322 -4.1667404
S -1.2045031 1.2624527 -2.9490191
C -0.5170233 2.7735147 1.7890395
H 0.1897341 2.5579946 0.9587402
H -0.1817476 3.6864329 2.3434608
S3
H -1.5092436 2.9968065 1.3360800
S -0.5859628 1.3069271 2.8986914
C -0.5055631 -1.6440394 4.3765240
H -1.3125977 -0.8903412 4.5041769
H 0.4429013 -1.1359999 4.6628636
H -0.6817372 -2.4716890 5.1124802
S -0.4582362 -2.2773941 2.6480953
Fe -0.5822491 -0.4261876 -1.2438221
Fe -0.4040092 -0.3452652 1.1749566
S 1.3672017 0.2724370 -0.2315191
C -2.0078868 0.0019752 0.0519971
H -0.5166457 -1.6358452 -0.0228939
H -2.3493298 1.0582445 -0.0027923
H -2.8433420 -0.7077099 0.2366894
Listing S4. HFe
2
B. Optimized with def2-TZVP/UKS-TPSS/DFTD3
27
HC, Energy = -5076.012745 H
C -1.89342031 -2.94949331 -7.12177899
H -2.54339731 -0.97906391 -7.09286332
H -3.30953872 -4.10746983 -6.13271285
H -1.78233191 -3.61259806 -9.09765127
S 1.20164028 -3.14391237 -5.53655396
C 0.70175561 3.31623544 -7.75340011
H 2.42278875 4.48645307 -7.75437981
H -0.55001429 4.01726270 -9.26916545
H 1.25567282 1.35936496 -8.16726945
S -0.88385618 3.42838856 -4.65419662
C -1.59341328 5.38738577 2.69823716
H -0.16329228 5.34717827 1.20448660
H -1.86184135 7.35300309 3.34781319
H -3.37275285 4.72943706 1.86139269
S -0.60598410 3.33049089 5.32345806
C -1.97412845 -2.92554715 7.85809788
H -1.77207663 -3.52650830 9.84758262
H -3.52264699 -4.03137012 7.01379265
H -2.50137471 -0.92207831 7.79977086
S 0.99725315 -3.37479862 6.08671301
Fe 1.00043688 0.01396551 -2.23952733
Fe 1.02807517 -0.20085270 2.85930267
S 4.26540766 0.81314534 0.32021427
C -1.93759727 -1.49377793 0.28393699
H -1.95616552 -3.56679309 0.32360730
H -2.89342485 -0.84128190 -1.46884922
H -3.10644747 -0.76171110 1.85525513
Listing S5. HC
27
HS, Energy = -5076.012745 H
C -2.28190831 -2.62210518 -7.76955353
H -2.56284663 -0.56787565 -7.85553475
H -4.03818994 -3.47510426 -7.05136733
H -1.94432387 -3.35920341 -9.69484777
S 0.40213316 -3.31569812 -5.65738597
C 1.57606301 3.29373354 -7.35844928
H 3.42391523 3.96597767 -6.68727406
H 1.01832504 4.44632529 -9.00859059
H 1.79096721 1.31185662 -7.93261306
S -0.79847573 3.47813910 -4.81583865
C -2.08354987 5.15638282 2.93197739
H -1.21863646 5.12371124 1.05214145
H -2.16709842 7.13010952 3.60467260
H -4.02585861 4.45405403 2.73259777
S -0.27975217 3.16867996 5.15203571
S4
C -1.59027439 -3.03107071 8.07979081
H -1.89832095 -0.98326605 8.17172587
H -0.97425784 -3.72263174 9.95295889
H -3.40997359 -3.94032514 7.63279479
S 0.79130768 -3.71820521 5.62317417
Fe -0.03478993 -0.25266009 -2.35732660
Fe 0.26452015 -0.52658586 2.52302989
S 3.94044001 0.17720368 -0.16367398
C -2.57249201 -1.25056306 0.19231189
H 3.82334645 2.70489675 0.20264152
H -4.27428958 -0.05798262 0.40347862
H -3.11427509 -3.26422004 0.14094785
Listing S6. HS
27
HFe , Energy = -5076.012745 H
C -3.75913157 -2.73243516 -5.62379855
H -3.29406598 -0.86937361 -6.40698422
H -5.34465440 -2.50613889 -4.30508511
H -4.33389115 -4.02169448 -7.16164635
S -0.94169345 -3.95902372 -4.00566722
C 3.36704638 0.78931871 -6.64033009
H 5.16356944 0.74240615 -5.59643989
H 3.70490535 1.68962586 -8.49608837
H 2.74508794 -1.16929167 -6.92812697
S 0.93491439 2.49051761 -4.84940786
C -1.68456058 7.18270902 2.40049702
H 0.19224944 6.49260250 1.86699529
H -1.50677428 9.06394023 3.29003486
H -2.79670363 7.39397233 0.65959374
S -3.19217575 4.89925564 4.56992044
C -2.19692263 -4.80564329 4.43881601
H -2.57539687 -4.92192958 2.40602069
H -3.03292045 -6.46935583 5.38725653
H -0.13958047 -4.84884165 4.68075772
S -3.48483113 -1.83709967 5.73824166
Fe 0.38826032 -0.59158352 -1.35560261
Fe -1.70350676 1.07471666 2.92488570
S 2.41535463 0.66757931 2.06352051
C -3.11193692 0.30561124 -0.38195714
H 2.67456217 -2.54093001 -1.48834688
H -3.80956887 2.12943289 -1.11041352
H -4.60333594 -1.13690125 -0.42009557
Listing S7. HFe
27
HFe2 , Energy = -5076.012745 H
C -1.10308696 -3.43573011 -8.31015755
H -1.97612529 -1.55868177 -8.47300817
H -2.14811060 -4.78815975 -9.50868326
H 0.84450816 -3.32220378 -9.04341854
S -1.16558991 -4.42709801 -4.97779147
C 1.01349275 2.98702318 -6.87382013
H 2.38288989 3.07635358 -5.32040867
H 1.08693632 4.76165870 -7.96939213
H 1.55847962 1.42276663 -8.12966587
S -2.15634240 2.50020374 -5.54907517
C -1.11945035 5.29777671 3.59413326
H 0.39205944 5.04544188 2.19778930
H -0.71668237 6.96183152 4.78580215
H -2.88709716 5.63793316 2.56070368
S -1.34233521 2.43107787 5.53953962
C -0.81834672 -3.19565308 8.30207207
H -2.35902855 -1.86830822 8.70843936
H 0.96112552 -2.20397624 8.69784276
H -0.97571351 -4.81794673 9.60760604
S -0.94162510 -4.27161064 4.99428938
Fe -1.11154921 -0.67337271 -2.32791573
Fe -0.91042029 -0.60040006 2.27934685