Supporting Information to accompany:

On the Inner Workings of Monte Carlo Codes

David Dubbeldam, Ariana Torres-Knoop

Van t Hoff Institute for Molecular Sciences, University of Amsterdam,
Science Park 904, 1098XH, Amsterdam, The Netherlands

Krista S. Walton,
School of Chemical & Biomolecular Engineering, Georgia Institute of Technology,
311 Ferst Dr. NW, Atlanta, GA 30332-0100, USA
June 9, 2013

email: D.Dubbeldam@uva.nl

S1
1 Triclinic vs. orthorhombic structures

p [Pa] mono ortho body-centered primitive

100 0.0000053(18) 0.00000507(57) 0.0000044(31) 0.0000048(15)
101 0.0000517(58) 0.0000503(18) 0.0000511(82) 0.000047(14)
102 0.000512(12) 0.000518(12) 0.000527(15) 0.000523(30)
103 0.005188(26) 0.005145(51) 0.005168(83) 0.00517(13)
104 0.05074(35) 0.05088(29) 0.05099(29) 0.05094(24)
105 0.4352(35) 0.4424(41) 0.4443(29) 0.4496(37)
106 1.9018(54) 1.9049(28) 1.8990(19) 1.8904(33)
107 2.6888(16) 2.68894(82) 2.6880(23) 2.6869(20)
108 3.0359(40) 3.0359(46) 3.0314(30) 3.0313(50)

a [A] 13.5292 23.4333 12.5573 9.2294

b [A] 13.5292 13.5292 12.5573 9.2294

c [A] 14.7483 14.7483 12.5573 9.2294
[ ] 90 90 65.1905 94.2676
[ ] 90 90 65.1905 94.2676
[ ] 120 90 65.1905 94.2676
rel. V 1 2 2/3 1/3

p [Pa] primitive 110 face-center A face-center B face-center C

100 0.00000520(43) 0.0000042(17) 0.0000047(19) 0.0000051(33)
101 0.0000519(45) 0.0000511(71) 0.0000518(79) 0.0000516(53)
102 0.000510(14) 0.000519(14) 0.000522(20) 0.0005117(89)
103 0.005165(78) 0.005154(95) 0.005153(59) 0.005167(86)
104 0.05090(41) 0.05079(18) 0.05089(37) 0.05084(49)
105 0.4408(16) 0.4448(42) 0.4456(18) 0.4454(53)
106 1.9059(20) 1.8989(30) 1.8985(70) 1.8994(35)
107 2.68891(37) 2.6881(19) 2.6875(19) 2.6884(18)
108 3.0349(45) 3.0332(98) 3.0356(38) 3.0334(53)

a [A] 9.2294 9.2294 12.5573 12.5573

b [A] 12.5573 12.5573 9.2294 13.5292

c [A] 20.0138 13.5292 13.5292 9.2294

[ ] 102.2882 90 90 90
[ ] 27.3789 90 90 96.2799
[ ] 83.7201 96.2799 96.2799 90
rel. V 1.852 2/3 2/3 2/3

Table S1: Methane adsorption isotherms at 298K in CHA, 333 unit cells; loadings in mol kg1 .

S2
2 Average energy of a single molecule

MD (2.5ns) MC trans. MC reins. (k=10) MC reins. (k=1) MC trans. + reins. (k=10)

25K -2056.8 0.2 -2056.8 0.1 -2056.8 0.2 -2056.7 0.1 -2056.7 0.1
50K -2013.5 0.7 -2013.7 0.1 -2013.7 0.3 -2013.7 0.2 -2013.6 0.2
100K -1912.9 0.8 -1913.1 0.3 -1913.3 0.4 -1913.4 0.3 -1913.2 0.6
200K -1692.8 3.0 -1691.9 0.7 -1692.3 0.5 -1692.1 0.3 -1692.1 0.5
300K -1529.7 8.3 -1530.8 1.2 -1531.3 0.6 -1531.2 0.3 -1531.0 0.7
400K -1423.7 12.8 -1419.8 0.6 -1420.1 0.4 -1420.3 0.3 -1420.2 0.5
500K -1348.0 7.0 -1340.9 1.1 -1341.2 0.3 -1341.3 0.1 -1341.5 0.6
600K -1281.1 13.1 -1282.5 1.3 -1282.4 1.0 -1282.5 0.3 -1282.7 0.8
700K -1235.4 14.7 -1236.9 0.7 -1236.9 1.1 -1237.0 0.4 -1237.0 0.8
800K -1197.1 5.4 -1200.2 1.7 -1200.8 0.2 -1200.5 0.3 -1200.5 0.4

Table S2: Methane in 2 2 4 unit cells of MgMOF-74 (a = b = 25.8765 A, = = 90 , = 120 ). MD

c = 6.7856 A,
runs with 256 molecules, inter-molecular interactions removed, Nose-Hoover thermostat, t = 0.0005; Total potential energies
given in Kelvin.

MD (2.5ns) MC trans. + rot. MC reins. (k=10)

25K -3091.9 50.0 -3364.5 20.5 -3367.3 3.2
50K -3147.0 105.2 -3295.4 0.3 -3285.3 3.3
100K -2993.9 35.7 -3038.1 134.5 -3056.2 1.7
200K -2494.7 6.0 -2494.7 3.4 -2495.5 2.5
300K -2056.0 15.4 -2052.4 3.0 -2053.3 0.6
400K -1815.0 18.2 -1816.6 2.6 -1816.4 0.9
500K -1678.9 16.5 -1680.3 1.8 -1680.1 1.0
600K -1605.3 13.7 -1590.8 1.7 -1591.2 0.5
700K -1533.5 7.8 -1527.0 1.3 -1528.1 1.0
800K -1483.8 12.4 -1478.3 1.5 -1478.2 0.7

Table S3: CO2 in 2 2 1 unit cells of DMOF (a = b = 21.624 A, c = 38.385 A, = = = 90 ). MD runs with 256
molecules, inter-molecular interactions removed, Nose-Hoover thermostat, t = 0.0005; Total potential energies given in Kelvin.

S3
3 Average potential energy of adorbates at finite loading in a nanoporous
material

MD Utotal MC Utotal MD Uhost-ads MC Uhost-ads MD Uads-ads MC Uads-ads

25K -170296.2 8.1 -169677.8 782.8 -120871.6 643.4 -119410.7 374.4 -49424.6 642.0 -50267.1 586.4
50K -166692.7 235.0 -166459.0 485.5 -117281.1 742.0 -117716.2 445.6 -49411.6 597.3 -48742.8 169.9
100K -159827.9 29.8 -159791.4 650.8 -114451.0 323.0 -113767.5 465.3 -45376.9 315.0 -46023.9 391.4
200K -146889.4 82.5 -146978.4 265.5 -107059.3 331.5 -107127.0 182.5 -39830.0 292.8 -39851.4 196.5
300K -135546.7 114.1 -135451.8 140.3 -101440.4 80.6 -101448.2 191.0 -34106.3 112.7 -34003.6 144.4
400K -125019.6 166.6 -124920.3 149.0 -96329.8 104.7 -96259.5 178.0 -28689.8 128.4 -28660.8 81.3
500K -115261.7 97.6 -115159.3 325.3 -91731.7 129.2 -91708.6 239.6 -23530.1 161.5 -23450.7 97.2
600K -105870.0 296.9 -105934.5 363.0 -87347.6 92.6 -87430.4 215.4 -18522.3 235.3 -18504.1 247.6
700K -97046.4 224.8 -97025.2 308.6 -83313.2 114.0 -83273.6 244.4 -13733.2 130.2 -13751.6 118.5
800K -88632.0 200.3 -88719.9 288.2 -79452.3 151.6 -79488.7 260.0 -9179.7 91.8 -9231.2 200.5

Table S4: Methane adosorbates in FAU (111 unit cell) at 12 molecules per supercage and 300K. MD uses the NVT ensemble
with the Nose-Hoover thermostat; time-step t = 0.0005 ps; total simulation 2.5 ns; energy conservation better than 2.5e-5. MC
uses 50000 initialization cycles; 5000000 cycles for production.

S4
4 NPT MC vs. MD

300K 400K 500K

p [bar] MC MD MC MD MC MD
10.64 490.5 5.8 486.5 5.1 15.1 0.2 15.1 0.6 11.7 0.4 11.5 0.3
21.28 495.3 3.0 496.5 4.6 32.0 1.3 32.6 1.1 23.9 0.8 23.7 1.0
31.91 496.9 5.3 503.9 8.9 53.1 1.6 54.3 2.7 37.1 0.6 37.1 1.4
42.55 497.5 4.4 502.6 6.5 81.0 3.8 81.1 4.0 51.1 1.0 51.1 2.6
53.19 501.4 4.3 503.6 5.2 115.7 14.3 127.4 6.3 65.3 1.0 66.0 3.5
63.83 503.3 3.1 506.5 7.8 183.8 50.8 164.3 11.7 81.1 3.9 80.1 2.2
74.47 509.6 2.9 507.5 6.4 245.5 31.7 262.1 22.4 96.2 2.0 99.9 3.0
85.11 510.3 2.0 508.7 6.8 298.4 3.2 311.0 11.3 114.9 3.7 117.7 8.2
95.74 511.9 4.9 517.1 4.6 323.0 21.9 318.5 13.5 130.6 5.8 134.2 4.0
106.38 514.7 6.5 518.2 5.4 338.1 8.7 345.0 13.2 151.8 6.3 153.9 10.0
117.02 517.8 4.9 518.7 4.8 359.4 6.7 357.1 9.6 168.2 7.7 174.5 15.7
127.66 519.0 5.2 522.4 7.2 363.4 15.3 371.6 10.0 184.6 2.9 186.1 8.4
138.30 521.1 5.3 521.1 6.1 378.2 8.0 375.9 9.2 203.0 4.5 199.3 8.6
148.94 523.9 2.1 525.0 7.5 384.6 6.9 377.1 5.6 221.4 2.2 215.1 6.0
159.57 525.7 2.8 529.2 5.0 395.0 6.1 393.9 11.4 232.9 2.9 235.6 8.2
170.21 527.2 5.0 526.4 5.8 392.0 14.0 393.8 10.8 247.0 6.6 250.6 4.0
180.85 528.9 1.8 530.8 2.2 407.1 4.7 406.8 3.3 258.6 7.5 258.0 10.3
191.49 530.7 5.4 531.9 4.2 407.4 6.7 412.0 9.6 271.3 5.7 272.3 2.8
202.13 532.4 3.4 534.1 4.5 413.9 11.3 418.8 7.9 283.4 6.1 278.7 16.4
212.77 534.2 5.7 530.8 3.9 421.0 3.0 421.6 9.1 293.0 3.2 297.3 9.7
223.40 535.8 1.0 536.0 4.7 424.1 5.8 420.3 5.8 298.2 7.5 304.8 5.6
234.04 535.8 3.2 535.5 4.8 428.6 3.7 428.3 3.7 307.3 2.9 307.8 10.2
244.68 537.7 3.2 540.7 5.8 433.0 3.7 439.0 6.1 314.9 8.7 315.1 10.5
255.32 540.5 3.3 540.6 3.1 435.4 3.5 436.8 5.6 323.0 0.7 320.7 9.7
265.96 542.4 3.4 541.4 5.3 440.4 3.8 436.1 12.2 329.9 7.2 325.4 12.0
276.60 542.4 4.2 545.4 7.6 442.0 2.5 438.4 11.7 332.6 4.1 337.8 9.6
287.23 545.3 3.0 546.7 3.9 444.6 2.0 444.1 3.2 338.8 5.3 343.9 6.4
297.87 545.8 1.7 546.3 3.0 448.8 4.4 447.2 5.2 344.6 8.2 348.8 7.7
308.51 548.3 4.0 546.9 5.8 450.6 7.7 454.4 5.2 348.9 2.6 354.0 4.4
319.15 550.2 2.6 544.7 2.5 454.1 3.3 455.4 6.4 358.0 5.9 359.2 10.4
329.79 550.2 4.0 549.0 6.0 458.6 3.3 457.3 11.2 362.6 5.5 360.3 8.0
340.43 552.4 2.9 551.6 4.1 458.1 5.1 458.7 1.4 366.3 5.1 368.1 4.8
351.06 550.9 1.9 551.2 5.5 463.2 3.1 462.7 8.0 369.9 2.5 371.2 4.5
361.70 554.0 4.1 552.5 1.9 464.3 5.6 463.3 5.7 377.9 7.2 375.5 8.3
372.34 553.9 2.3 554.2 4.7 466.9 4.6 466.8 7.1 375.5 10.1 377.0 8.1
382.98 554.7 2.9 553.0 5.5 468.8 2.8 470.2 3.0 380.5 4.4 381.0 5.2
393.62 557.9 4.0 556.4 7.1 471.3 2.5 473.0 6.0 384.2 5.5 386.0 7.6
404.26 558.4 2.5 557.2 2.3 473.3 2.0 470.0 5.9 390.7 3.9 390.2 7.2
414.89 560.7 1.6 559.6 1.3 473.7 4.2 476.4 3.1 391.0 6.8 392.2 6.3
425.53 560.1 3.9 563.0 0.9 477.6 1.9 478.8 3.9 400.1 3.9 398.0 2.6
436.17 562.2 5.1 563.2 1.5 478.9 3.8 481.6 2.6 399.4 5.2 400.4 5.4
446.81 563.7 2.7 564.6 3.6 479.9 2.6 481.9 4.1 401.5 4.2 399.9 6.5
457.45 565.0 2.5 564.2 4.9 482.8 4.5 480.4 4.5 404.9 3.4 406.5 4.2
468.09 566.3 3.0 566.4 3.0 485.0 1.1 485.0 2.8 407.6 4.2 406.7 2.7
478.72 566.7 3.0 565.1 2.7 487.0 2.1 488.8 3.2 410.2 5.4 405.8 2.5
489.36 567.4 3.2 568.8 1.3 488.1 3.7 487.5 3.7 414.5 1.9 411.7 9.2
500.00 568.8 1.9 568.7 1.8 490.4 4.8 494.3 4.9 415.5 3.4 412.8 4.2

Table S5: NPT simulation of propane comparing MC to MD. Densities in kg m3 .

S5
5 Bond-length, bend-angle, and dihedral-angle distributions

MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC
Relative probability, P /

Relative probability, P /

Relative probability, P /
0.8 1 1.2 1.4 1.6 1.8 0.8 1 1.2 1.4 1.6 1.8 0.8 1 1.2 1.4 1.6 1.8
Bond length 01, l / Bond length 04, l / Bond length 03, l /

MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC
Relative probability, P /

Relative probability, P /

Relative probability, P /
0.8 1 1.2 1.4 1.6 1.8 0.8 1 1.2 1.4 1.6 1.8 0.8 1 1.2 1.4 1.6 1.8
Bond length 04, l / Bond length 45, l / Bond length 46, l /

MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC
Relative probability, P /

Relative probability, P /

Relative probability, P /
0.8 1 1.2 1.4 1.6 1.8 0.8 1 1.2 1.4 1.6 1.8 0.8 1 1.2 1.4 1.6 1.8
Bond length 47, l / Bond length 78, l / Bond length 79, l /

MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC
Relative probability, P /

Relative probability, P /

Relative probability, P /

0.8 1 1.2 1.4 1.6 1.8 0.8 1 1.2 1.4 1.6 1.8 0.8 1 1.2 1.4 1.6 1.8
Bond length 713, l / Bond length 910, l / Bond length 911, l /

MD 1024 molec. MD 1024 molec.

CBMC CBMC
Relative probability, P /

Relative probability, P /

0.8 1 1.2 1.4 1.6 1.8 0.8 1 1.2 1.4 1.6 1.8
Bond length 912, l / Bond length 1314, l /

Figure S1: Bond length distributions for S2-butanol, CBMC compared to MD at 300K.

S6
 MD 1024 molec. MD 1024 molec. MD 1024 molec. MD 1024 molec.
CBMC CBMC CBMC CBMC
Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

Relative probability, P / -
80 90 100 110 120 130 80 90 100 110 120 130 80 90 100 110 120 130 80 90 100 110 120 130
Bend angle 1-0-2, / degrees Bend angle 1-0-3, / degrees Bend angle 1-0-4, / degrees Bend angle 2-0-3, / degrees

MD 1024 molec. MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC CBMC
Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

Relative probability, P / -
80 90 100 110 120 130 80 90 100 110 120 130 80 90 100 110 120 130 80 90 100 110 120 130
Bend angle 2-0-4, / degrees Bend angle 3-0-4, / degrees Bend angle 0-4-5, / degrees Bend angle 0-4-6, / degrees

MD 1024 molec. MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC CBMC
Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

Relative probability, P / -
80 90 100 110 120 130 80 90 100 110 120 130 80 90 100 110 120 130 80 90 100 110 120 130
Bend angle 0-4-7, / degrees Bend angle 5-4-6, / degrees Bend angle 5-4-7, / degrees Bend angle 6-4-7, / degrees

MD 1024 molec. MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC CBMC
Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

Relative probability, P / -
80 90 100 110 120 130 80 90 100 110 120 130 80 90 100 110 120 130 80 90 100 110 120 130
Bend angle 4-7-8, / degrees Bend angle 4-7-9, / degrees Bend angle 4-7-13, / degrees Bend angle 8-7-9, / degrees

MD 1024 molec. MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC CBMC
Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

80 90 100 110 120 130 80 90 100 110 120 130 80 90 100 110 120 130 80 90 100 110 120 130
Bend angle 8-7-13, / degrees Bend angle 9-7-13, / degrees Bend angle 7-9-10, / degrees Bend angle 7-9-11, / degrees

MD 1024 molec. MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC CBMC
Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

80 90 100 110 120 130 80 90 100 110 120 130 80 90 100 110 120 130 80 90 100 110 120 130
Bend angle 7-9-12, / degrees Bend angle 10-9-11, / degrees Bend angle 10-9-12, / degrees Bend angle 11-9-12, / degrees

MD 1024 molec. MD 1024 molec.

CBMC CBMC
Relative probability, P / -

Relative probability, P / -

80 90 100 110 120 130 80 90 100 110 120 130

Bend angle 11-9-12, / degrees Bend angle 7-13-14, / degrees

Figure S2: Bend angle distributions for S2-butanol, CBMC compared to MD at 300K.

S7
 MD 1024 molec. MD 1024 molec. MD 1024 molec. MD 1024 molec.
CBMC CBMC CBMC CBMC

Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

Relative probability, P / -
0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350
Dihedral angle 1-0-4-5, / degrees Dihedral angle 1-0-4-6, / degrees Dihedral angle 1-0-4-7, / degrees Dihedral angle 2-0-4-5, / degrees

MD 1024 molec. MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC CBMC
Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

Relative probability, P / -
0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350
Dihedral angle 2-0-4-6, / degrees Dihedral angle 2-0-4-7, / degrees Dihedral angle 3-0-4-5, / degrees Dihedral angle 3-0-4-6, / degrees

MD 1024 molec. MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC CBMC
Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

Relative probability, P / -
0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350
Dihedral angle 3-0-4-7, / degrees Dihedral angle 0-4-7-8, / degrees Dihedral angle 0-4-7-9, / degrees Dihedral angle 0-4-7-13, / degrees

MD 1024 molec. MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC CBMC
Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

Relative probability, P / -
0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350
Dihedral angle 5-4-7-8, / degrees Dihedral angle 5-4-7-9, / degrees Dihedral angle 5-4-7-13, / degrees Dihedral angle 6-4-7-8, / degrees

MD 1024 molec. MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC CBMC
Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350
Dihedral angle 6-4-7-9, / degrees Dihedral angle 6-4-7-13, / degrees Dihedral angle 4-7-9-10, / degrees Dihedral angle 4-7-9-11, / degrees

MD 1024 molec. MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC CBMC
Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350
Dihedral angle 4-7-9-12, / degrees Dihedral angle 8-7-9-10, / degrees Dihedral angle 8-7-9-11, / degrees Dihedral angle 8-7-9-12, / degrees

MD 1024 molec. MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC CBMC
Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350
Dihedral angle 8-7-9-12, / degrees Dihedral angle 13-7-9-10, / degrees Dihedral angle 13-7-9-11, / degrees Dihedral angle 13-7-9-12, / degrees

MD 1024 molec. MD 1024 molec. MD 1024 molec.

CBMC CBMC CBMC
Relative probability, P / -

Relative probability, P / -

Relative probability, P / -

0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350 0 50 100 150 200 250 300 350
Dihedral angle 4-7-13-14, / degrees Dihedral angle 8-7-13-14, / degrees Dihedral angle 9-7-13-14, / degrees

Figure S3: Dihedral distributions for S2-butanol, CBMC compared to MD at 300K.

S8
 16
Absolute loading, q / mol. kg-1

14

12

10
CO2, N2 pure (Toth fit)
8 IAST prediction
CO2 pure
6 N2 pure
CO2 mixture
4 N2 mixture

0
0 2 4 6 8 10 12
Bulk fluid phase fugacity, f / bar
Figure S4: IAST prediction of the equimolar CO2 /N2 -mixture based on the pure components, compared to the mixture simulation
results, at 300K. The pure components were fitted with the Toth-isotherm-type.

S9