An All-Atom Force Field Developed for Zn4o(RCO2)6Metalorganic Frameworks

Supporting Information

An all-atom force field developed for Zn4O(RCO2)6metalorganic frameworks

Yingxin Sun*†,and Huai Sun*††

†School of Chemical and Environmental Engineering, Shanghai Institute of Technology,

††School of Chemistry and Chemical Engineering and Key Laboratory for Thin Film and Microfabrication of Ministry of Education,Shanghai Jiao Tong University, Shanghai 200240, China

E-mail:,and

Table S1Bond force field parameters for MOFs

Bond Stretching
bond / b0 (Å) / kb (kJmol-1Å-2)
c_3 — c_3ab / 1.4635 / 1670.746
c_3 — h_1 / 1.1005 / 1540.788
c_3 — o_2 / 1.2714 / 2941.706
c_34a— c_34a / 1.3970 / 1829.480
c_34a — c_3ab / 1.3793 / 2154.484
c_34a — c_44 / 1.5155 / 1321.507
c_3a — c_3a / 1.3915 / 2067.730
c_3a — c_3ab / 1.3927 / 2056.320
c_3a — c_4h2 / 1.4784 / 1626.279
c_3a — h_1 / 1.0836 / 1729.102
c_3ab— c_3ab / 1.4381 / 1918.872
c_44 —c_44 / 1.5904 / 1106.018
c_44 — h_1 / 1.0941 / 1591.046
c_4h2 —c_4h2 / 1.5314 / 1289.469
c_4h2 — h_1 / 1.0961 / 1559.928
o_2 — zn4o / 1.9693 / 453.702
o_4 — zn4o / 2.0961 / 212.627

Table S2Angleforce field parameters for MOFs

Angle Bending
angle / θ0 (deg) / ka (kJmol-1rad-2)
c_3—c_3ab—c_34a / 121.9635 / 223.333
c_3—c_3ab—c_3a / 116.0631 / 197.499
c_3—o_2—zn4o / 134.5354 / 56.804
c_34a—c_34a—c_3ab / 121.9418 / 221.991
c_34a—c_34a—c_44 / 93.6091 / 354.108
c_34a—c_3ab—c_3a / 115.9884 / 261.182
c_34a—c_44—c_44 / 86.4038 / 398.629
c_34a—c_44—h_1 / 115.4423 / 185.676
c_3a—c_3a—c_3a / 118.3566 / 285.996
c_3a—c_3a—c_3ab / 118.5211 / 278.343
c_3a—c_3a—c_4h2 / 124.6658 / 121.260
c_3a—c_3a—h_1 / 123.2891 / 138.659
c_3a—c_3ab—c_3a / 122.9102 / 228.548
c_3a —c_3ab —c_3ab / 124.3554 / 206.670
c_3a—c_4h2—c_4h2 / 114.6940 / 356.386
c_3a —c_4h2 —h_1 / 107.9851 / 193.054
c_3ab —c_3 —o_2 / 116.8364 / 239.609
c_3ab —c_34a —c_44 / 144.3747 / 50.359
c_3ab —c_3a —c_3ab / 120.3816 / 323.197
c_3ab —c_3a —h_1 / 117.5168 / 132.563
c_44 —c_44 —h_1 / 115.1490 / 191.324
c_4h2 —c_4h2 —h_1 / 109.2929 / 203.514
h_1 —c_3 —o_2 / 113.5271 / 225.566
h_1 —c_44 —h_1 / 108.2249 / 122.693
h_1 —c_4h2 —h_1 / 106.5843 / 151.484
o_2 —c_3 —o_2 / 128.4073 / 436.804
o_2 —zn4o —o_2 / 111.9475 / 110.066
o_2 —zn4o —o_4 / 107.7932 / 71.085
zn4o —o_4 —zn4o / 109.5522 / 201.134

Table S3 Dihedral angle force field parameters for MOFs

Dihedral Angle
angle / n / kt (kJmol-1)
c_3 —c_3ab —c_34a —c_34a / 2 / 20.361
c_3—c_3ab—c_34a—c_44 / 2 / 5.971
c_3 —c_3ab —c_3a —c_3a / 2 / 23.178
c_3 —c_3ab —c_3a —h_1 / 2 / 11.457
c_3—o_2—zn4o—o_2 / 3 / -0.101
c_3—o_2—zn4o—o_4 / 3 / -1.799
c_34a —c_34a —c_3ab —c_3a / 2 / 20.364
c_34a—c_34a—c_44—c_44 / 2 / 22.780
c_34a—c_34a—c_44—h_1 / 3 / -3.231
c_34a —c_3ab —c_3 —o_2 / 2 / 4.368
c_34a —c_3ab —c_3a —c_3a / 2 / 12.498
c_34a —c_3ab —c_3a —h_1 / 2 / 11.806
c_34a—c_44—c_44—c_34a / 2 / 35.432
c_34a—c_44—c_44—h_1 / 3 / -2.670
c_3a —c_3a —c_3a —c_3a / 2 / 19.598
c_3a —c_3a —c_3a —c_3ab / 2 / 16.374
c_3a —c_3a —c_3a —c_4h2 / 2 / 27.110
c_3a —c_3a —c_3a —h_1 / 2 / 17.776
c_3a —c_3a —c_3ab —c_3a / 2 / 15.921
c_3a —c_3a —c_3ab —c_3ab / 2 / 17.754
c_3a —c_3a —c_4h2 —c_4h2 / 3 / -12.801
c_3a —c_3ab —c_3 —o_2 / 2 / 4.689
c_3a —c_3ab —c_34a —c_44 / 2 / 11.950
c_3a —c_3ab —c_3a —c_3ab / 2 / 12.959
c_3a —c_3ab —c_3a —h_1 / 2 / 14.680
c_3a —c_3ab —c_3ab —c_3a / 2 / 2.976
c_3a —c_4h2 —c_4h2 —c_3a / 3 / 25.173
c_3a —c_4h2 —c_4h2 —h_1 / 3 / 9.970
c_3ab —c_3 —o_2 —zn4o / 2 / 4.630
c_3ab—c_34a—c_34a—c_3ab / 2 / 8.065
c_3ab —c_34a —c_34a —c_44 / 2 / 13.768
c_3ab—c_34a—c_44—c_44 / 2 / -13.859
c_3ab —c_34a —c_44 —h_1 / 3 / -1.720
c_3ab—c_3a—c_3a—c_3ab / 2 / 15.179
c_3ab —c_3a —c_3a —c_4h2 / 2 / 5.387
c_3ab —c_3a —c_3a —h_1 / 2 / 15.358
c_3ab —c_3a —c_3ab —c_3ab / 2 / 19.097
c_3ab —c_3ab —c_3a —h_1 / 2 / 6.384
c_44 —c_34a —c_34a —c_44 / 2 / 27.496
c_4h2 —c_3a —c_3a —h_1 / 2 / 4.967
h_1 —c_3 —o_2 —zn4o / 2 / 7.052
h_1 —c_3a —c_3a —h_1 / 2 / 7.044
h_1 —c_44 —c_44 —h_1 / 3 / 0.568
o_2 —c_3 —o_2 —zn4o / 2 / 1.066
o_2 —zn4o —o_4 —zn4o / 3 / -5.605
c_3a —c_3a —c_4h2 —h_1 / 1 / -5.515
2 / 1.297
3 / 3.648
h_1 —c_4h2 —c_4h2 —h_1 / 1 / 8.135
2 / 0.182
3 / -0.832

Table S4Out-of-planeangle force field parameters for MOFs

Out-of-Plane Angle
angle / χ0 / k0 (kJmol-1rad-2)
c_3 —c_3ab —c_34a —c_3a / 0 / 9.760
c_3 —c_3ab —c_3a —c_3a / 0 / 10.839
c_34a —c_34a —c_3ab —c_44 / 0 / 13.303
c_3a —c_3a —c_3a —c_3a / 0 / 41.840
c_3a —c_3a —c_3a —c_4h2 / 0 / 5.283
c_3a —c_3a —c_3a —h_1 / 0 / 9.751
c_3a —c_3a —c_3ab —h_1 / 0 / 18.284
c_3a —c_3ab —c_3a —c_3ab / 0 / 23.013
c_3ab—c_3—o_2—o_2 / 0 / 41.840
c_3ab—c_3a—c_3ab—h_1 / 0 / 22.737

Table S5Bond-bond cross couplingforce field parameters for MOFs

Bond-Bond Cross Coupling
angle / bond / bond / kbb (kJmol-1Å-2)
c_3—c_3ab—c_34a / c_3 —c_3ab / c_3ab —c_34a / 257.876
c_3—c_3ab—c_3a / c_3 —c_3ab / c_3ab —c_3a / 287.050
c_3—o_2—zn4o / c_3—o_2 / o_2—zn4o / 303.302
c_34a—c_34a—c_3ab / c_34a —c_34a / c_34a —c_3ab / 531.851
c_34a—c_34a—c_44 / c_34a—c_34a / c_34a—c_44 / 171.835
c_34a—c_3ab—c_3a / c_34a —c_3ab / c_3ab —c_3a / 614.227
c_34a—c_44—c_44 / c_34a—c_44 / c_44—c_44 / 42.098
c_34a—c_44—h_1 / c_34a—c_44 / c_44—h_1 / 48.893
c_3a—c_3a—c_3a / c_3a —c_3a / c_3a —c_3a / 581.641
c_3a—c_3a—c_3ab / c_3a —c_3a / c_3a —c_3ab / 587.420
c_3a—c_3a—c_4h2 / c_3a —c_3a / c_3a —c_4h2 / 191.750
c_3a—c_3a—h_1 / c_3a—c_3a / c_3a—h_1 / 131.720
c_3a—c_3ab—c_3a / c_3a —c_3ab / c_3ab —c_3a / 628.201
c_3a —c_3ab —c_3ab / c_3a —c_3ab / c_3ab —c_3ab / 229.770
c_3a—c_4h2—c_4h2 / c_3a —c_4h2 / c_4h2 —c_4h2 / 102.963
c_3a—c_4h2—h_1 / c_3a—c_4h2 / c_4h2—h_1 / 41.964
c_3ab—c_3—o_2 / c_3ab—c_3 / c_3—o_2 / 407.307
c_3ab—c_34a—c_44 / c_3ab —c_34a / c_34a —c_44 / 131.071
c_3ab —c_3a —c_3ab / c_3ab —c_3a / c_3a —c_3ab / 570.290
c_3ab—c_3a—h_1 / c_3ab —c_3a / c_3a —h_1 / 135.116
c_44—c_44—h_1 / c_44—c_44 / c_44—h_1 / 25.941
c_4h2—c_4h2—h_1 / c_4h2—c_4h2 / c_4h2—h_1 / 32.643
h_1—c_44—h_1 / h_1—c_44 / c_44—h_1 / 12.908
h_1—c_4h2—h_1 / h_1—c_4h2 / c_4h2—h_1 / 9.625
o_2—c_3—o_2 / o_2—c_3 / c_3—o_2 / 870.687
o_2—zn4o—o_2 / o_2 —zn4o / zn4o —o_2 / 127.582
o_2—zn4o—o_4 / o_2 —zn4o / zn4o —o_4 / 95.706
zn4o—o_4—zn4o / zn4o —o_4 / o_4 —zn4o / 63.410

Table S6 Bond-anglecross coupling force field parameters for MOFs

Bond-Angle Cross Coupling
angle / bond / angle / kba (kJmol-1Å-1rad-1)
c_3—c_3ab—c_34a / c_3 —c_3ab / c_3 —c_3ab —c_34a / 98.794
c_3ab —c_34a / c_3 —c_3ab —c_34a / -17.683
c_3—c_3ab—c_3a / c_3 —c_3ab / c_3 —c_3ab —c_3a / 78.385
c_3ab —c_3a / c_3 —c_3ab —c_3a / -29.184
c_3—o_2—zn4o / c_3 —o_2 / c_3 —o_2 —zn4o / 51.255
o_2 —zn4o / c_3 —o_2 —zn4o / 64.659
c_34a—c_34a—c_3ab / c_34a —c_34a / c_34a —c_34a —c_3ab / -87.286
c_34a —c_3ab / c_34a —c_34a —c_3ab / 11.431
c_34a—c_34a—c_44 / c_34a —c_34a / c_34a —c_34a —c_44 / 98.882
c_34a —c_44 / c_34a —c_34a —c_44 / 417.264
c_34a—c_3ab—c_3a / c_34a —c_3ab / c_34a —c_3ab —c_3a / 40.614
c_3ab —c_3a / c_34a —c_3ab —c_3a / -25.906
c_34a—c_44—c_44 / c_34a —c_44 / c_34a —c_44 —c_44 / 260.642
c_44—c_44 / c_34a—c_44—c_44 / 518.961
c_34a—c_44—h_1 / c_34a —c_44 / c_34a —c_44 —h_1 / 87.703
c_44—h_1 / c_34a—c_44—h_1 / 87.997
c_3a—c_3a—c_3a / c_3a —c_3a / c_3a —c_3a —c_3a / -18.124
c_3a—c_3a—c_3ab / c_3a —c_3a / c_3a —c_3a —c_3ab / 3.588
c_3a —c_3ab / c_3a —c_3a —c_3ab / 2.325
c_3a—c_3a—c_4h2 / c_3a —c_3a / c_3a —c_3a —c_4h2 / -43.661
c_3a —c_4h2 / c_3a —c_3a —c_4h2 / 221.794
c_3a—c_3a—h_1 / c_3a —c_3a / c_3a —c_3a —h_1 / 53.801
c_3a —h_1 / c_3a —c_3a —h_1 / 105.793
c_3a—c_3ab—c_3a / c_3a —c_3ab / c_3a —c_3ab —c_3a / -28.780
c_3a —c_3ab —c_3ab / c_3a —c_3ab / c_3a —c_3ab —c_3ab / 71.934
c_3ab —c_3ab / c_3a —c_3ab —c_3ab / 236.852
c_3a—c_4h2—c_4h2 / c_3a —c_4h2 / c_3a —c_4h2 —c_4h2 / 139.855
c_4h2 —c_4h2 / c_3a —c_4h2 —c_4h2 / 188.733
c_3a—c_4h2—h_1 / c_3a —c_4h2 / c_3a —c_4h2 —h_1 / 143.907
c_4h2 —h_1 / c_3a —c_4h2 —h_1 / 111.579
c_3ab—c_3—o_2 / c_3ab —c_3 / c_3ab —c_3 —o_2 / 248.471
c_3 —o_2 / c_3ab —c_3 —o_2 / 338.932
c_3ab—c_34a—c_44 / c_3ab —c_34a / c_3ab —c_34a —c_44 / -74.474
c_34a —c_44 / c_3ab —c_34a —c_44 / 27.660
c_3ab —c_3a —c_3ab / c_3ab —c_3a / c_3ab —c_3a —c_3ab / 17.559
c_3ab—c_3a—h_1 / c_3ab —c_3a / c_3ab —c_3a —h_1 / 39.217
c_3a —h_1 / c_3ab —c_3a —h_1 / 139.549
c_44—c_44—h_1 / c_44—c_44 / c_44—c_44—h_1 / 73.093
c_44—h_1 / c_44—c_44—h_1 / 86.458
c_4h2—c_4h2—h_1 / c_4h2 —c_4h2 / c_4h2 —c_4h2 —h_1 / 126.264
c_4h2 —h_1 / c_4h2 —c_4h2 —h_1 / 117.060
h_1—c_44—h_1 / h_1—c_44 / h_1—c_44—h_1 / 128.537
h_1—c_4h2—h_1 / h_1 —c_4h2 / h_1 —c_4h2 —h_1 / 116.124
o_2—c_3—o_2 / o_2—c_3 / o_2—c_3—o_2 / 297.057
o_2—zn4o—o_2 / o_2 —zn4o / o_2 —zn4o —o_2 / 80.866
o_2—zn4o—o_4 / o_2 —zn4o / o_2 —zn4o —o_4 / 2.242
zn4o —o_4 / o_2 —zn4o —o_4 / 39.166
zn4o—o_4—zn4o / zn4o —o_4 / zn4o —o_4 —zn4o / 146.440

TableS7 Comparison of calculated values of (m2 s-1) and (kJ mol-1) for benzene and n-hexane diffusions in different flexible MOFs

MOFs / guests / (250K) / (300K) / (350K) / (400K) /
IRMOF-1 / benzene / 2.28E-09 / 5.60E-09 / 8.64E-09 / 1.45E-08 / 9.96
IRMOF-1 / n-hexane / 1.78E-09 / 4.48E-09 / 7.37E-09 / 1.04E-08 / 9.84
IRMOF-6 / benzene / 9.53E-10 / 2.46E-09 / 5.68E-09 / 9.18E-09 / 12.92
IRMOF-6 / n-hexane / 1.10E-09 / 2.74E-09 / 4.67E-09 / 7.43E-09 / 10.52
IRMOF-8 / benzene / 1.57E-09 / 3.62E-09 / 7.97E-09 / 1.25E-08 / 11.66
IRMOF-8 / n-hexane / 2.14E-09 / 4.36E-09 / 7.07E-09 / 1.14E-08 / 9.17
IRMOF-10 / benzene / 2.60E-09 / 6.33E-09 / 1.23E-08 / 1.89E-08 / 11.05
IRMOF-10 / n-hexane / 3.01E-09 / 6.40E-09 / 1.19E-08 / 1.94E-08 / 10.27
IRMOF-12 / benzene / 4.23E-10 / 1.46E-09 / 3.69E-09 / 6.92E-09 / 15.59
IRMOF-12 / n-hexane / 2.03E-09 / 3.69E-09 / 6.00E-09 / 1.05E-08 / 8.95
IRMOF-14 / benzene / 1.57E-09 / 3.19E-09 / 7.38E-09 / 1.07E-08 / 11.01
IRMOF-14 / n-hexane / 2.05E-09 / 3.56E-09 / 7.10E-09 / 1.06E-08 / 9.33
IRMOF-16 / benzene / 1.36E-09 / 3.49E-09 / 1.42E-08 / 2.66E-08 / 16.46
IRMOF-16 / n-hexane / 2.26E-09 / 6.81E-09 / 1.31E-08 / 1.98E-08 / 12.05
MOF-C30 / benzene / 1.70E-09 / 4.43E-09 / 8.59E-09 / 9.23E-09 / 10.58
MOF-C30 / n-hexane / 2.92E-09 / 3.26E-09 / 5.97E-09 / 9.50E-09 / 6.57
MOF-177 / benzene / 2.99E-09 / 4.99E-09 / 1.18E-08 / 2.77E-08 / 12.26
MOF-177 / n-hexane / 2.76E-09 / 8.44E-09 / 1.29E-08 / 1.55E-08 / 9.93

TableS8 Comparison of calculated values of (m2 s-1) and (kJ mol-1) for benzene and n-hexane diffusions in different rigid MOFs

MOFs / guests / (250K) / (300K) / (350K) / (400K) /
IRMOF-1 / benzene / 1.98E-09 / 4.23E-09 / 6.61E-09 / 1.04E-08 / 9.10
IRMOF-1 / n-hexane / 1.50E-09 / 3.43E-09 / 5.60E-09 / 8.26E-09 / 9.46
IRMOF-6 / benzene / 1.71E-10 / 5.60E-10 / 8.79E-10 / 1.76E-09 / 13.35
IRMOF-6 / n-hexane / 4.25E-10 / 9.42E-10 / 1.62E-09 / 2.73E-09 / 10.18
IRMOF-8 / benzene / 9.49E-10 / 2.92E-09 / 4.44E-09 / 7.73E-09 / 11.43
IRMOF-8 / n-hexane / 1.15E-09 / 2.32E-09 / 4.12E-09 / 6.49E-09 / 9.61
IRMOF-10 / benzene / 2.07E-09 / 4.56E-09 / 7.82E-09 / 1.32E-08 / 10.08
IRMOF-10 / n-hexane / 1.77E-09 / 4.04E-09 / 7.35E-09 / 1.30E-08 / 10.95
IRMOF-12 / benzene / 2.03E-10 / 7.19E-10 / 2.24E-09 / 4.04E-09 / 16.92
IRMOF-12 / n-hexane / 1.06E-09 / 2.38E-09 / 3.90E-09 / 6.42E-09 / 9.78
IRMOF-14 / benzene / 1.31E-09 / 3.15E-09 / 5.09E-09 / 8.39E-09 / 10.22
IRMOF-14 / n-hexane / 1.36E-09 / 2.92E-09 / 4.81E-09 / 7.48E-09 / 9.35
IRMOF-16 / benzene / 6.37E-10 / 2.57E-09 / 6.86E-09 / 1.38E-08 / 16.97
IRMOF-16 / n-hexane / 1.12E-09 / 3.04E-09 / 5.54E-09 / 1.25E-08 / 13.15
MOF-C30 / benzene / 1.80E-09 / 3.56E-09 / 6.24E-09 / 8.17E-09 / 9.77
MOF-C30 / n-hexane / 1.03E-09 / 1.96E-09 / 3.28E-09 / 5.06E-09 / 8.26
MOF-177 / benzene / 2.49E-09 / 5.87E-09 / 7.11E-09 / 1.97E-08 / 10.64
MOF-177 / n-hexane / 2.54E-09 / 5.01E-09 / 1.02E-08 / 1.40E-08 / 9.82

(a) (b)

(c) (d)

Figure S1. Atomic power spectra of IRMOF-1 with and without the cross coupling force field parameters for atom types zn4o, o_4, o_2, and c_3 at 300 K. (a) zn4o; (b) o_4; (c) o_2; (d) c_3.

(a) (b)

Figure S2. Arrhenius-type plot of Dself versus T-1 for benzene diffusions in different MOFs. (a) flexible model (b) rigid model. Solid lines represent linear regressions from each of MOFs.

(a) (b)

Figure S3. Arrhenius-type plot of Dself versus T-1 for n-hexane diffusions in MOFs. (a) flexible model (b) rigid model. Solid lines represent linear regressions from each of MOFs.