Supplementary Material for:

Solvent Effects on IR Modes of (R)-3-methylcyclopentanone Conformers: a Computational Investigation

Watheq Al-Basheer

Departments of Physics, University of Tennessee, Knoxville, TN 37996 and

Center for Atmospheric Research Experiments, Environment Canada, Egbert, ON L0L 1N0, Canada

Table A1 DFT calculations of the IR spectra of R3MCP equatorial (eq.) and axial (ax.) conformers

in cyclohexane (C6H12) using B3LYP functions with basis sets aug-cc-pVDZ

eq. R3MCP in cyclohexane (C6H12) solution / ax. R3MCP in cyclohexane (C6H12) solution
eq. n (cm–1) / IR intensity (arbitrary units) / ax. n (cm–1) / IR intensity (arbitrary units)
86.5973 / 8.1871 / 76.7736 / 6.9148
165.0224 / 0.3377 / 162.0877 / 0.8319
232.7847 / 0.1122 / 233.3818 / 0.1141
280.4011 / 1.6413 / 345.7813 / 1.4066
407.3136 / 0.6055 / 363.2284 / 0.944
455.9307 / 0.7581 / 453.7316 / 2.8211
485.5335 / 10.9256 / 473.4726 / 8.7737
536.4248 / 6.0087 / 579.9653 / 7.5494
582.0019 / 5.6697 / 662.6701 / 2.9772
720.2420 / 1.9231 / 730.8737 / 2.2057
811.7345 / 3.8507 / 790.1567 / 2.8718
840.0155 / 0.4484 / 813.2336 / 2.1831
880.7792 / 5.3018 / 876.2484 / 4.9492
928.5226 / 0.7004 / 929.2320 / 2.0197
938.3116 / 2.2893 / 951.2377 / 1.1137
991.0614 / 1.6622 / 992.5618 / 0.9339
994.6960 / 2.896 / 1003.5563 / 0.6142
1084.9849 / 12.7302 / 1031.8847 / 7.7275
1140.5469 / 0.1324 / 1108.3252 / 1.8387
1155.1603 / 29.7053 / 1159.714 / 53.6413
1165.5837 / 41.9488 / 1165.9311 / 27.4162
1206.5913 / 1.5461 / 1192.5871 / 0.1034
1239.4281 / 0.0385 / 1218.5563 / 1.8657
1254.7568 / 15.6212 / 1257.7094 / 6.67
1288.5784 / 3.2018 / 1281.9515 / 6.7571
1300.6620 / 5.7632 / 1307.3169 / 1.7656
1331.4839 / 2.9273 / 1329.0585 / 2.8813
1370.8759 / 4.5792 / 1362.1628 / 2.217
1392.5732 / 5.8236 / 1394.1174 / 6.8765
1426.6089 / 19.6011 / 1427.7669 / 26.5496
1430.6586 / 4.5907 / 1432.0004 / 1.1143
1468.3165 / 2.671 / 1470.6942 / 3.9889
1473.1949 / 7.0894 / 1474.0603 / 5.964
1482.5508 / 5.6736 / 1486.7327 / 4.9683
1779.8481 / 368.1853 / 1777.7913 / 352.7438
2997.8490 / 4.7943 / 3021.4416 / 29.2388
3009.8254 / 15.2400 / 3025.0421 / 6.4262
3018.5489 / 24.2801 / 3037.9999 / 6.0328
3026.1917 / 5.8051 / 3040.0299 / 21.7393
3030.5012 / 53.0638 / 3053.7445 / 29.25
3085.6802 / 23.0265 / 3089.9295 / 35.4818
3091.4480 / 47.3552 / 3090.3348 / 32.6209
3093.9333 / 28.2801 / 3096.1298 / 4.3377
3100.1207 / 12.2653 / 3099.0735 / 43.2212
3102.3136 / 18.3985 / 3102.4283 / 19.1644

Table A2 DFT calculations of the IR spectra of R3MCP equatorial (eq.) and axial (ax.) conformers in carbon tetrachloride (CCl4) using B3LYP functions with basis sets aug-cc-pVDZ

eq. R3MCP in carbon tetrachloride (CCl4) solution / ax. R3MCP in carbon tetrachloride (CCl4) solution
eq. n (cm–1) / IR intensity (arbitrary units) / ax. n (cm–1) / IR intensity (arbitrary units)
86.9479 / 8.5404 / 77.9264 / 7.249
164.8939 / 0.3479 / 162.2761 / 0.7958
232.7742 / 0.1155 / 233.2792 / 0.1244
280.4304 / 1.7064 / 345.9991 / 1.4665
407.2290 / 0.6227 / 363.2259 / 0.9912
455.9907 / 0.7733 / 454.0430 / 2.9753
485.6410 / 11.2887 / 473.4026 / 8.9765
536.4546 / 6.2882 / 579.9552 / 7.8372
581.9669 / 5.9611 / 663.8731 / 3.108
720.0899 / 1.9259 / 730.3496 / 2.204
812.0454 / 3.8886 / 790.2752 / 2.9449
840.0641 / 0.4571 / 813.4096 / 2.1726
880.5979 / 5.4781 / 876.2818 / 5.2179
928.4762 / 0.7375 / 929.1717 / 1.9793
938.1225 / 2.3558 / 950.8544 / 1.1258
990.9388 / 1.7325 / 992.7354 / 1.0321
994.5406 / 2.9385 / 1003.4680 / 0.6677
1085.1270 / 12.872 / 1031.8584 / 7.8107
1140.5253 / 0.1168 / 1107.5991 / 2.0229
1155.2751 / 29.7524 / 1159.5884 / 50.4883
1165.8567 / 43.6478 / 1165.9068 / 32.512
1206.3313 / 1.5917 / 1192.6200 / 0.1252
1239.4531 / 0.0436 / 1218.5256 / 1.9316
1254.9692 / 16.1922 / 1257.8897 / 6.775
1288.5740 / 3.2233 / 1281.7532 / 7.2005
1300.6404 / 6.0102 / 1307.2816 / 1.7287
1331.2503 / 2.9959 / 1328.9484 / 2.9123
1370.7828 / 4.6311 / 1362.1121 / 2.2161
1392.2519 / 5.8416 / 1393.8151 / 6.923
1425.7937 / 20.234 / 1427.0038 / 27.1712
1429.7710 / 4.5427 / 1431.1456 / 1.0919
1468.0013 / 2.7216 / 1470.2137 / 4.073
1472.8409 / 7.1333 / 1473.8697 / 6.0287
1482.0746 / 5.7372 / 1486.4045 / 5.0103
1777.1449 / 380.3666 / 1776.2542 / 364.9727
2996.7976 / 4.7979 / 3020.5437 / 29.3472
3008.8643 / 15.225 / 3022.8897 / 6.5579
3018.3229 / 24.7169 / 3037.1681 / 6.4365
3025.3794 / 4.04 / 3039.5353 / 20.6784
3029.9560 / 54.9311 / 3052.9138 / 30.0994
3085.4972 / 23.4652 / 3089.4340 / 39.749
3091.1565 / 46.6707 / 3089.9442 / 27.693
3093.7188 / 28.887 / 3095.8575 / 3.7605
3099.2036 / 12.2091 / 3098.6631 / 42.3458
3101.4607 / 18.9013 / 3101.2677 / 21.8776

Table A3 DFT calculations of the IR spectra of R3MCP equatorial (eq.) and axial (ax.) conformers in toluene (C7H8) using B3LYP functions with basis sets aug-cc-pVDZ

eq. R3MCP in toluene (C7H8) solution / ax. R3MCP in toluene (C7H8) solution
eq. n (cm–1) / IR intensity (arbitrary units) / ax. n (cm–1) / IR intensity (arbitrary units)
87.0686 / 8.7747 / 77.4386 / 7.3819
164.9208 / 0.3527 / 162.1099 / 0.8965
232.8067 / 0.1181 / 233.4244 / 0.1181
280.4472 / 1.75 / 345.7130 / 1.5095
407.1719 / 0.629 / 363.1965 / 1.0067
456.0446 / 0.7859 / 453.8911 / 2.9964
485.6481 / 11.4743 / 473.7948 / 9.2247
536.4565 / 6.4686 / 579.8866 / 8.2212
581.9729 / 6.1227 / 662.3811 / 3.0566
719.9788 / 1.9326 / 730.6566 / 2.2475
812.2447 / 3.904 / 790.3935 / 2.9219
840.1080 / 0.4556 / 813.5518 / 2.2552
880.4880 / 5.6113 / 875.9265 / 5.1899
928.4397 / 0.7611 / 929.0385 / 2.0701
937.9824 / 2.4078 / 950.9694 / 1.2017
990.8944 / 1.7936 / 992.2015 / 0.9728
994.4811 / 2.9673 / 1003.4303 / 0.6422
1085.2239 / 12.986 / 1031.7816 / 7.9032
1140.5080 / 0.1135 / 1107.9560 / 1.9935
1155.3655 / 29.7607 / 1160.1493 / 53.0771
1166.0006 / 44.7576 / 1166.2333 / 31.5436
1206.1800 / 1.6244 / 1192.4777 / 0.115
1239.4703 / 0.0463 / 1218.2857 / 1.9728
1255.1056 / 16.5788 / 1257.8902 / 7.0045
1288.5823 / 3.2358 / 1281.7841 / 7.369
1300.6861 / 6.1603 / 1307.4685 / 1.8185
1331.1528 / 3.0345 / 1328.9706 / 3.0109
1370.7521 / 4.6613 / 1362.0148 / 2.2679
1392.0561 / 5.8505 / 1393.6805 / 6.8377
1425.2624 / 20.5902 / 1426.4798 / 27.6253
1429.2151 / 4.5996 / 1430.6455 / 1.2287
1467.8006 / 2.7578 / 1470.1745 / 4.0682
1472.6253 / 7.1584 / 1473.4782 / 6.0464
1481.7998 / 5.7689 / 1485.9618 / 5.052
1775.4435 / 388.1919 / 1773.3711 / 372.3076
2996.1053 / 4.808 / 3020.8632 / 29.9851
3008.2242 / 15.2236 / 3023.8522 / 6.1343
3018.1605 / 24.9942 / 3036.6243 / 6.5092
3024.8498 / 3.2894 / 3039.2597 / 20.5592
3029.6168 / 55.7662 / 3052.4041 / 30.2214
3085.3611 / 23.8375 / 3089.3512 / 39.0623
3090.9487 / 46.1437 / 3089.9024 / 28.9058
3093.5595 / 29.2289 / 3094.8472 / 3.8391
3098.6419 / 12.0813 / 3098.5477 / 42.7372
3100.8639 / 19.3696 / 3101.3088 / 21.1568

Table A4 DFT calculations of the IR spectra of R3MCP equatorial (eq.) and axial (ax.) conformers in benzene (C6H6) using B3LYP functions with basis sets aug-cc-pVDZ

eq. R3MCP in benzene (C6H6) solution / ax. R3MCP in benzene (C6H6) solution
eq. n (cm–1) / IR intensity (arbitrary units) / ax. n (cm–1) / IR intensity (arbitrary units)
86.9894 / 8.5694 / 78.0399 / 7.2438
164.9654 / 0.3445 / 162.5600 / 0.8163
232.7387 / 0.1155 / 233.4615 / 0.1215
280.3914 / 1.7122 / 345.9734 / 1.4803
407.2241 / 0.6226 / 363.2804 / 0.9995
456.0319 / 0.7783 / 454.1383 / 2.9884
485.6358 / 11.3191 / 473.5309 / 9.0166
536.4647 / 6.3113 / 579.9458 / 7.9601
581.9306 / 5.9862 / 663.4571 / 3.1207
720.0652 / 1.9275 / 730.5085 / 2.2256
812.0704 / 3.8892 / 790.3056 / 2.9527
840.0620 / 0.4613 / 813.4516 / 2.1689
880.5688 / 5.4998 / 876.2257 / 5.2051
928.4535 / 0.7463 / 929.1379 / 1.9956
938.0812 / 2.3692 / 950.9653 / 1.1387
990.9207 / 1.7482 / 992.6173 / 1.0226
994.5265 / 2.9334 / 1003.4263 / 0.6548
1085.1485 / 12.8832 / 1031.8424 / 7.8238
1140.5097 / 0.1157 / 1107.7185 / 2.0237
1155.2612 / 29.6195 / 1159.7279 / 51.0484
1165.8569 / 43.9261 / 1165.9815 / 32.1915
1206.3062 / 1.5907 / 1192.5775 / 0.1164
1239.4503 / 0.0442 / 1218.4829 / 1.9175
1254.9770 / 16.2438 / 1257.9234 / 6.8392
1288.5609 / 3.219 / 1281.8076 / 7.2218
1300.5982 / 6.0378 / 1307.3400 / 1.7562
1331.2176 / 3.0023 / 1328.9626 / 2.922
1370.7898 / 4.636 / 1362.1020 / 2.2213
1392.2242 / 5.8443 / 1393.7929 / 6.8987
1425.7126 / 20.2901 / 1426.9750 / 27.2216
1429.6787 / 4.54 / 1431.1189 / 1.072
1467.9709 / 2.73 / 1470.2385 / 4.0763
1472.8145 / 7.1424 / 1473.8017 / 6.0283
1482.0417 / 5.7327 / 1486.3281 / 5.013
1776.8895 / 381.4714 / 1775.4742 / 366.3092
2996.6610 / 4.813 / 3020.6095 / 29.8492
3008.7564 / 15.2184 / 3023.1061 / 6.0942
3018.3127 / 24.7569 / 3036.9816 / 6.4001
3025.3011 / 3.893 / 3039.3784 / 20.717
3029.9185 / 55.1097 / 3052.7086 / 30.1183
3085.4927 / 23.6035 / 3089.3432 / 39.4814
3091.1723 / 46.5877 / 3089.8659 / 28.1953
3093.7186 / 28.9242 / 3095.5746 / 3.5641
3099.1830 / 12.1822 / 3098.5915 / 42.5873
3101.4530 / 18.8774 / 3101.2337 / 21.6048

Table A5 DFT calculations of the IR spectra of R3MCP equatorial (eq.) and axial (ax.) conformers in chlorobenzene (C6H5Cl) using B3LYP functions with basis sets aug-cc-pVDZ

eq. R3MCP in chlorobenzene (C6H5Cl) solution / ax. R3MCP in chlorobenzene (C6H5Cl) solution
eq. n (cm–1) / IR intensity (arbitrary units) / ax. n (cm–1) / IR intensity (arbitrary units)
88.1957 / 11.6153 / 81.7549 / 9.5636
164.7464 / 0.6406 / 163.5623 / 1.1405
233.0131 / 0.1463 / 233.7023 / 0.1419
280.8371 / 2.2167 / 345.7542 / 1.9834
406.0885 / 0.7346 / 363.1841 / 1.3029
457.0490 / 0.8759 / 454.6501 / 3.775
486.2022 / 13.8183 / 474.7814 / 11.5132
535.9068 / 8.7028 / 579.3302 / 11.2133
581.7093 / 8.1839 / 662.4014 / 3.5319
718.9721 / 2.0324 / 729.4286 / 2.4135
814.3751 / 3.9724 / 791.1513 / 3.1762
840.3249 / 0.4933 / 815.0684 / 2.4216
879.0169 / 7.1037 / 874.8054 / 6.5433
928.2475 / 1.0629 / 928.3413 / 2.2246
936.7947 / 2.9598 / 949.7586 / 1.6137
989.9603 / 2.3054 / 991.1790 / 1.2127
993.4074 / 3.43 / 1002.7701 / 0.8297
1085.8570 / 14.1152 / 1031.3242 / 8.6871
1140.1087 / 0.1519 / 1105.9612 / 2.8845
1155.8923 / 29.4905 / 1161.1312 / 43.9833
1167.4409 / 56.7989 / 1167.2704 / 55.6985
1204.4818 / 2.1156 / 1192.0771 / 0.3461
1239.3542 / 0.1651 / 1217.1662 / 2.5172
1256.5674 / 20.9142 / 1258.5959 / 8.3463
1288.4542 / 3.3413 / 1281.0308 / 10.5639
1300.6130 / 8.1244 / 1307.9774 / 1.9794
1329.5207 / 3.4498 / 1328.6378 / 3.5297
1369.9121 / 4.9902 / 1361.3784 / 2.4208
1389.9055 / 5.8728 / 1391.7286 / 6.5626
1419.7491 / 24.5697 / 1421.2797 / 31.6397
1423.3245 / 4.8482 / 1425.1858 / 2.0953
1465.6441 / 3.1473 / 1467.9011 / 4.4308
1470.3458 / 7.3024 / 1471.3483 / 6.4849
1478.3097 / 6.0336 / 1482.8751 / 5.2013
1757.4395 / 474.5097 / 1756.7170 / 458.4123
2988.9507 / 4.736 / 3015.4284 / 18.6273
3001.4764 / 14.9177 / 3019.5427 / 18.7233
3016.1978 / 27.0426 / 3029.4963 / 9.821
3017.6572 / 2.9639 / 3035.6591 / 13.9015
3026.6060 / 58.1456 / 3047.0294 / 35.1915
3084.0248 / 27.0082 / 3086.3377 / 34.7904
3088.5819 / 37.374 / 3087.5866 / 32.0387
3091.9045 / 32.6988 / 3089.0250 / 4.462
3092.0335 / 14.0896 / 3095.7673 / 21.0126
3095.4640 / 26.1375 / 3097.6176 / 47.6309

Table A6 DFT calculations of the IR spectra of R3MCP equatorial (eq.) and axial (ax.) conformers in chloroform (CHCl3) using B3LYP functions with basis sets aug-cc-pVDZ

eq. R3MCP in chloroform (CHCl3) solution / ax. R3MCP in chloroform (CHCl3) solution
eq. n (cm–1) / IR intensity (arbitrary units) / ax. n (cm–1) / IR intensity (arbitrary units)
88.1610 / 11.2489 / 81.8690 / 9.3946
164.3985 / 0.4183 / 164.5611 / 1.0461
232.5244 / 0.1403 / 233.6019 / 0.1477
280.5244 / 2.1572 / 345.9481 / 1.9509
406.3569 / 0.7218 / 363.4304 / 1.2896
456.6590 / 0.8901 / 455.1783 / 3.8442
486.0637 / 13.5996 / 474.6166 / 10.766
536.2283 / 8.3308 / 579.3264 / 10.8225
581.6422 / 7.9405 / 663.4564 / 3.6019
781.9490 / 2.0144 / 729.4203 / 2.3996
813.9810 / 4.0098 / 791.1696 / 3.2195
840.2529 / 0.4988 / 815.0057 / 2.3332
879.2812 / 6.9048 / 875.1974 / 6.5086
928.1156 / 1.0412 / 928.2756 / 2.1612
936.7991 / 2.8748 / 949.7510 / 1.5065
989.9962 / 2.2621 / 991.4740 / 1.2882
993.6250 / 3.3089 / 1002.7621 / 0.8405
1085.9101 / 13.923 / 1031.2968 / 8.5184
1140.1200 / 0.1347 / 1105.6206 / 2.8804
1155.8324 / 29.5175 / 1160.6486 / 41.9425
1167.2444 / 55.3468 / 1167.1822 / 55.6048
1204.6582 / 1.9666 / 1192.0516 / 0.2533
1239.3449 / 0.1327 / 1217.3158 / 2.3983
1256.1756 / 20.3759 / 1258.5971 / 8.0453
1288.3530 / 3.3309 / 1281.1770 / 10.2551
1300.5409 / 7.8144 / 1307.7315 / 1.8896
1329.7195 / 3.4074 / 1328.5378 / 3.394
1370.0944 / 4.9501 / 1361.4499 / 2.3673
1390.1396 / 5.8761 / 1391.9248 / 6.642
1420.2690 / 24.2527 / 1421.9220 / 31.2651
1423.8412 / 4.5715 / 1425.7608 / 1.5861
1465.9238 / 3.0944 / 1468.0425 / 4.4679
1470.5753 / 7.3023 / 1471.7495 / 6.3802
1478.8093 / 6.004 / 1483.3756 / 5.1827
1759.7421 / 463.9764 / 1758.9371 / 448.7278
2989.5874 / 4.8449 / 3014.9434 / 17.6231
3002.2256 / 14.9453 / 3019.5847 / 19.3609
3016.7592 / 28.1977 / 3029.8269 / 9.7449
3019.1693 / 1.0717 / 3036.0686 / 14.3168
3027.0231 / 58.4879 / 3047.5310 / 34.9495
3084.3235 / 27.5517 / 3086.5458 / 34.5529
3089.2475 / 38.6828 / 3087.6903 / 32.3177
3092.2952 / 33.989 / 3090.0697 / 4.1577
3093.6206 / 11.1525 / 3095.9657 / 22.0966
3096.4223 / 24.9334 / 3097.6767 / 46.4062

Table A7 DFT calculations of the IR spectra of R3MCP equatorial (eq.) and axial (ax.) conformers in dimethyl sulfoxide (C2H6OS) using B3LYP functions with basis sets aug-cc-pVDZ