Charcterization of Rotameric Mixtures in o- and m-Substituted Benzaldehydes by Matrix Isolation IR Spectroscopy by Pawel Bednarek, Thomas Bally,* and Jerzy Gebicki SUPPORTING INFORMATION ********************** Total energies, cartesian coordinates, vibrational frequencies and IR intensities ans well as thermal corrections for all stationary points located in this study. All results refer to B3LYP/6-31G* calculations --------------------------------------------------------------------------- 1. o-chlorobenzaldehyde trans rotamer SCF Done: E(RB+HF-LYP) = -805.165193084 X Y Z 6 2.394928 0.223263 0.000000 6 1.329929 1.114489 0.000000 6 0.000000 0.660573 0.000000 6 -0.227395 -0.724869 0.000000 6 0.832486 -1.630704 0.000000 6 2.142348 -1.152159 0.000000 6 -1.087449 1.675717 0.000000 8 -0.877547 2.874366 0.000000 17 -1.862761 -1.382288 0.000000 1 3.416387 0.591748 0.000000 1 1.486309 2.188869 0.000000 1 0.628487 -2.696011 0.000000 1 2.966588 -1.859994 0.000000 1 -2.119531 1.281483 0.000000 Low frequencies --- -9.6467 -5.2211 0.0020 0.0027 0.0029 2.7124 Low frequencies --- 118.2566 144.0457 205.0135 1 2 3 A" A" A' Frequencies -- 118.2563 144.0447 205.0135 IR Inten -- 4.3720 5.0377 3.5483 4 5 6 A" A' A' Frequencies -- 243.2685 295.1862 415.3771 IR Inten -- 3.7479 2.4896 12.8510 7 8 9 A" A' A" Frequencies -- 453.4034 487.6347 507.0629 IR Inten -- 3.9093 1.6276 0.8061 10 11 12 A' A" A' Frequencies -- 642.8233 716.0697 722.5998 IR Inten -- 13.4464 0.0584 20.3087 13 14 15 A" A' A" Frequencies -- 777.6522 839.0902 888.2657 IR Inten -- 49.4126 29.9919 0.0057 16 17 18 A" A" A" Frequencies -- 973.3513 1002.7204 1033.4386 IR Inten -- 1.5882 0.0058 0.1684 19 20 21 A' A' A' Frequencies -- 1055.4476 1072.3107 1145.9795 IR Inten -- 42.3398 11.5673 9.2193 22 23 24 A' A' A' Frequencies -- 1194.8293 1225.8681 1297.0126 IR Inten -- 3.8799 43.2630 53.0809 25 26 27 A' A' A' Frequencies -- 1347.5617 1442.6845 1486.0526 IR Inten -- 0.6579 25.7302 28.7122 28 29 30 A' A' A' Frequencies -- 1509.9899 1623.4499 1647.4386 IR Inten -- 18.8802 9.5670 57.7761 31 32 33 A' A' A' Frequencies -- 1790.1290 3004.1508 3197.4615 IR Inten -- 208.6857 65.9458 2.9170 34 35 36 A' A' A' Frequencies -- 3211.2769 3223.1881 3227.5618 IR Inten -- 8.9655 4.8352 6.5378 Zero-point correction= 0.100621 (Hartree/Particle) Thermal correction to Energy= 0.108112 Thermal correction to Enthalpy= 0.109057 Thermal correction to Gibbs Free Energy= 0.067891 --------------------------------------------------------------------------- 2. o-chlorobenzaldehyde cis rotamer SCF Done: E(RB+HF-LYP) = -805.160857973 X Y Z 6 2.420008 -0.799354 0.000000 6 1.206335 -1.477074 0.000000 6 -0.024006 -0.797590 0.000000 6 0.000000 0.611501 0.000000 6 1.213418 1.299889 0.000000 6 2.418153 0.596455 0.000000 6 -1.242559 -1.649904 0.000000 8 -2.396957 -1.280859 0.000000 17 -1.463695 1.568471 0.000000 1 3.355838 -1.349776 0.000000 1 1.190784 -2.564934 0.000000 1 1.206178 2.384604 0.000000 1 3.355303 1.146049 0.000000 1 -0.997735 -2.736609 0.000000 Low frequencies --- -0.0029 -0.0025 -0.0015 6.4349 7.7782 9.5806 Low frequencies --- 81.0545 176.2884 204.1337 1 2 3 A" A" A' Frequencies -- 81.0539 176.2881 204.1335 IR Inten -- 3.2985 2.8265 2.3907 4 5 6 A" A' A' Frequencies -- 250.9870 329.8519 369.2459 IR Inten -- 4.4856 4.1491 1.2390 7 8 9 A" A' A" Frequencies -- 446.1666 504.4646 521.6361 IR Inten -- 1.2349 6.5045 0.2551 10 11 12 A' A' A" Frequencies -- 665.5462 692.6444 719.2730 IR Inten -- 16.0602 22.6927 0.0079 13 14 15 A" A' A" Frequencies -- 773.2723 858.7665 884.3645 IR Inten -- 51.3590 34.5856 0.1240 16 17 18 A" A" A" Frequencies -- 958.2123 997.4726 1026.2189 IR Inten -- 1.5672 0.0802 0.0076 19 20 21 A' A' A' Frequencies -- 1068.0065 1080.5759 1162.4938 IR Inten -- 29.0378 25.4098 7.3377 22 23 24 A' A' A' Frequencies -- 1198.2023 1215.7475 1293.2005 IR Inten -- 2.6657 59.8772 8.7357 25 26 27 A' A' A' Frequencies -- 1352.6242 1456.2082 1487.7400 IR Inten -- 18.4576 20.4457 8.2550 28 29 30 A' A' A' Frequencies -- 1516.2385 1622.2760 1648.9534 IR Inten -- 29.4781 22.3713 45.8799 31 32 33 A' A' A' Frequencies -- 1814.5889 2895.9943 3181.9507 IR Inten -- 211.0116 129.5839 4.9936 34 35 36 A' A' A' Frequencies -- 3199.8787 3216.6198 3227.7664 IR Inten -- 5.3154 15.1872 5.1289 Zero-point correction= 0.100464 (Hartree/Particle) Thermal correction to Energy= 0.107947 Thermal correction to Enthalpy= 0.108891 Thermal correction to Gibbs Free Energy= 0.067706 ---------------------------------------------------------------------------- 3. m-chlorobenzaldehyde trans rotamer SCF Done: E(RB+HF-LYP) = -805.168048759 X Y Z 6 0.011826 -1.991682 0.000000 6 1.217068 -1.297832 0.000000 6 1.211158 0.104315 0.000000 6 0.000000 0.806619 0.000000 6 -1.196883 0.095514 0.000000 6 -1.203939 -1.299581 0.000000 6 2.488706 0.858593 0.000000 8 3.589533 0.344615 0.000000 1 0.005396 -3.077857 0.000000 1 2.171594 -1.814158 0.000000 17 -2.722423 0.968007 0.000000 1 -2.147730 -1.834608 0.000000 1 2.375169 1.965070 0.000000 1 -0.007112 1.892845 0.000000 Low frequencies --- -4.4595 -0.0046 -0.0032 -0.0027 6.4178 8.5889 Low frequencies --- 103.0941 176.8644 203.7816 1 2 3 A" A' A" Frequencies -- 103.0922 176.8641 203.7812 IR Inten -- 6.1644 7.0436 0.1186 4 5 6 A" A' A' Frequencies -- 241.0935 302.1578 399.6077 IR Inten -- 7.7472 2.9480 3.7429 7 8 9 A" A' A" Frequencies -- 439.4370 455.9859 526.8872 IR Inten -- 1.2013 0.6068 0.0382 10 11 12 A' A" A' Frequencies -- 661.1458 689.9590 734.7823 IR Inten -- 7.6265 10.2426 60.9814 13 14 15 A" A' A" Frequencies -- 808.0491 879.6390 899.4684 IR Inten -- 35.3107 31.1430 8.6781 16 17 18 A" A" A' Frequencies -- 937.1683 996.2995 1015.6407 IR Inten -- 0.0006 0.2709 2.2915 19 20 21 A" A' A' Frequencies -- 1033.7354 1101.1624 1128.7139 IR Inten -- 0.3299 18.1540 9.3170 22 23 24 A' A' A' Frequencies -- 1194.3422 1224.8353 1322.1835 IR Inten -- 16.8704 113.6685 16.9649 25 26 27 A' A' A' Frequencies -- 1361.6556 1426.9994 1474.8209 IR Inten -- 4.4906 15.6240 10.1589 28 29 30 A' A' A' Frequencies -- 1522.2981 1629.2531 1648.9292 IR Inten -- 13.5440 49.2127 7.4366 31 32 33 A' A' A' Frequencies -- 1804.5810 2918.7141 3202.1559 IR Inten -- 231.2589 121.7303 7.5369 34 35 36 A' A' A' Frequencies -- 3208.7903 3225.1014 3229.6158 IR Inten -- 0.7102 0.5102 5.3862 Zero-point correction= 0.100533 (Hartree/Particle) Thermal correction to Energy= 0.108017 Thermal correction to Enthalpy= 0.108961 Thermal correction to Gibbs Free Energy= 0.067756 ----------------------------------------------------------------------------- 4. m-chlorobenzaldehyde cis rotamer SCF Done: E(RB+HF-LYP) = -805.167986460 X Y Z 6 -0.419750 -2.120268 0.000000 6 -1.511105 -1.252350 0.000000 6 -1.302238 0.131459 0.000000 6 0.000000 0.652577 0.000000 6 1.074689 -0.226186 0.000000 6 0.879448 -1.611607 0.000000 6 -2.461916 1.056420 0.000000 8 -2.377202 2.268335 0.000000 1 -0.573545 -3.195369 0.000000 1 -2.525734 -1.643522 0.000000 17 2.713964 0.406314 0.000000 1 1.736576 -2.276721 0.000000 1 -3.454050 0.553573 0.000000 1 0.142210 1.727755 0.000000 Low frequencies --- -7.9378 -4.1439 -0.0047 -0.0044 -0.0043 1.2028 Low frequencies --- 122.8873 161.5569 174.6911 1 2 3 A" A' A" Frequencies -- 122.8873 161.5569 174.6904 IR Inten -- 4.5070 3.5143 0.7670 4 5 6 A" A' A' Frequencies -- 251.7066 327.4871 412.5231 IR Inten -- 4.5549 4.5776 6.5817 7 8 9 ?A ?A A" Frequencies -- 447.2104 447.5819 526.7023 IR Inten -- 1.9633 3.5144 0.1324 10 11 12 A' A" A' Frequencies -- 657.2894 690.3881 701.7236 IR Inten -- 13.5683 9.9840 55.5891 13 14 15 A" A' A" Frequencies -- 799.6028 910.3962 922.5262 IR Inten -- 35.2706 16.3945 0.1928 16 17 18 A" A" A' Frequencies -- 926.8522 986.3041 1015.9754 IR Inten -- 8.7469 0.0872 1.8265 19 20 21 A" A' A' Frequencies -- 1032.7368 1101.4038 1122.1558 IR Inten -- 0.3595 22.1749 0.1216 22 23 24 A' A' A' Frequencies -- 1198.3562 1223.9191 1309.1589 IR Inten -- 13.6310 133.0232 5.4922 25 26 27 A' A' A' Frequencies -- 1362.4055 1432.0087 1479.1905 IR Inten -- 4.1830 32.6940 22.9344 28 29 30 A' A' A' Frequencies -- 1516.9726 1630.9263 1648.1306 IR Inten -- 15.0643 28.0038 8.7548 31 32 33 A' A' A' Frequencies -- 1803.8512 2918.3330 3189.5452 IR Inten -- 222.1322 133.9317 3.9623 34 35 36 A' A' A' Frequencies -- 3208.5132 3228.1773 3235.1371 IR Inten -- 11.0823 3.9654 2.3773 Zero-point correction= 0.100523 (Hartree/Particle) Thermal correction to Energy= 0.107994 Thermal correction to Enthalpy= 0.108938 Thermal correction to Gibbs Free Energy= 0.067743 ---------------------------------------------------------------------------- 5. o-cyanobenzaldehyde trans rotamer SCF Done: E(RB+HF-LYP) = -437.812268395 X Y Z 6 2.351635 0.015755 0.000000 6 1.348674 0.980517 0.000000 6 0.000000 0.607741 0.000000 6 -0.335432 -0.764636 0.000000 6 0.679119 -1.735025 0.000000 6 2.015310 -1.342037 0.000000 6 -1.045432 1.667787 0.000000 8 -0.788263 2.855650 0.000000 6 -1.704817 -1.197588 0.000000 7 -2.805373 -1.574760 0.000000 1 3.395184 0.316780 0.000000 1 1.580917 2.040788 0.000000 1 0.410913 -2.786412 0.000000 1 2.795631 -2.097366 0.000000 1 -2.093275 1.309240 0.000000 Low frequencies --- 0.0002 0.0007 0.0007 4.5591 6.3220 11.6248 Low frequencies --- 118.2998 137.9379 141.9460 1 2 3 A" ?A ?A Frequencies -- 118.2930 137.9351 141.9460 IR Inten -- 0.6025 11.2586 5.4072 4 5 6 A" A' A" Frequencies -- 229.4517 234.2668 393.5913 IR Inten -- 2.9160 3.9372 1.0341 7 8 9 A' A" A' Frequencies -- 416.9474 464.0768 474.6608 IR Inten -- 0.1903 4.9483 6.3227 10 11 12 A" A' A' Frequencies -- 574.7950 598.0224 650.5289 IR Inten -- 6.8816 3.6718 11.2261 13 14 15 A" A' A" Frequencies -- 737.8545 784.4841 787.2666 IR Inten -- 2.6407 10.8965 43.3415 16 17 18 A' A" A" Frequencies -- 842.3286 907.4962 980.8845 IR Inten -- 25.7772 0.0058 1.4506 19 20 21 A" A" A' Frequencies -- 1012.8675 1036.9386 1065.8417 IR Inten -- 0.0380 0.2651 0.4419 22 23 24 A' A' A' Frequencies -- 1114.6470 1195.9030 1213.8129 IR Inten -- 4.8795 2.2394 2.4805 25 26 27 A' A' A' Frequencies -- 1232.8806 1304.2835 1355.3157 IR Inten -- 55.1013 28.5842 0.7175 28 29 30 A' A' A' Frequencies -- 1442.8881 1493.3314 1522.9222 IR Inten -- 9.6712 5.8537 4.8655 31 32 33 A' A' A' Frequencies -- 1623.7924 1648.6719 1798.7479 IR Inten -- 1.0689 34.3466 188.8690 34 35 36 A' A' A' Frequencies -- 2345.2817 2979.0434 3200.3653 IR Inten -- 15.5915 59.8750 1.4306 37 38 39 A' A' A' Frequencies -- 3212.8033 3224.0761 3227.7114 IR Inten -- 7.7519 2.6218 8.1575 Zero-point correction= 0.108730 (Hartree/Particle) Thermal correction to Energy= 0.116816 Thermal correction to Enthalpy= 0.117760 Thermal correction to Gibbs Free Energy= 0.075544 ----------------------------------------------------------------------------- 6. o-cyanobenzaldehyde cis rotamer SCF Done: E(RB+HF-LYP) = -437.808831126 X Y Z 6 2.308420 -0.959664 0.000000 6 1.044573 -1.547260 0.000000 6 -0.116514 -0.767511 0.000000 6 0.000000 0.642539 0.000000 6 1.274789 1.228014 0.000000 6 2.419854 0.431341 0.000000 6 -1.426856 -1.465179 0.000000 8 -2.510134 -0.920719 0.000000 6 -1.132877 1.525307 0.000000 7 -1.957952 2.344933 0.000000 1 3.199097 -1.580831 0.000000 1 0.946675 -2.630432 0.000000 1 1.357698 2.309917 0.000000 1 3.398879 0.901369 0.000000 1 -1.343947 -2.574324 0.000000 Low frequencies --- -9.9615 -5.3142 -0.0004 0.0002 0.0005 5.4622 Low frequencies --- 81.2031 156.7241 159.3277 1 2 3 A" ?A ?A Frequencies -- 81.1951 156.7238 159.3276 IR Inten -- 0.9537 6.4250 0.5711 4 5 6 ?A ?A ?A Frequencies -- 223.7698 235.5645 392.4561 IR Inten -- 13.7782 2.3718 0.1540 7 8 9 ?A A" A' Frequencies -- 397.9119 461.7255 523.0760 IR Inten -- 2.7421 4.3748 1.6887 10 11 12 A' A" A' Frequencies -- 559.5438 582.8566 674.8110 IR Inten -- 0.2786 4.6940 16.0857 13 14 15 A' A" A" Frequencies -- 736.5187 742.6794 783.1951 IR Inten -- 12.9846 4.7311 43.1207 16 17 18 A' A" A" Frequencies -- 874.8517 901.8744 968.9336 IR Inten -- 25.8250 0.0654 1.5869 19 20 21 A" A" A' Frequencies -- 1007.1051 1028.8393 1071.3319 IR Inten -- 0.0252 0.0993 0.6991 22 23 24 A' A' A' Frequencies -- 1136.5039 1200.5622 1219.9389 IR Inten -- 6.9800 0.1487 10.5441 25 26 27 A' A' A' Frequencies -- 1228.5260 1302.5444 1355.7014 IR Inten -- 48.3386 1.5605 23.0283 28 29 30 A' A' A' Frequencies -- 1444.0168 1491.3742 1531.6162 IR Inten -- 6.0320 1.6530 14.2834 31 32 33 A' A' A' Frequencies -- 1622.9827 1653.4549 1811.0741 IR Inten -- 24.4162 4.9331 170.4195 34 35 36 A' A' A' Frequencies -- 2348.0896 2917.8403 3187.4813 IR Inten -- 4.4994 126.5372 4.0189 37 38 39 A' A' A' Frequencies -- 3203.4743 3216.2962 3226.6328 IR Inten -- 3.5668 11.4853 6.8734 Zero-point correction= 0.108583 (Hartree/Particle) Thermal correction to Energy= 0.116685 Thermal correction to Enthalpy= 0.117629 Thermal correction to Gibbs Free Energy= 0.075356 ----------------------------------------------------------------------------- 7. m-cyanobenzaldehyde trans rotamer SCF Done: E(RB+HF-LYP) = -437.814063247 X Y Z 6 -0.339375 -1.938929 0.000000 6 0.941287 -1.394208 0.000000 6 1.113519 -0.001491 0.000000 6 0.000000 0.841006 0.000000 6 -1.291280 0.292683 0.000000 6 -1.457035 -1.103046 0.000000 6 2.479128 0.581202 0.000000 8 3.500808 -0.075128 0.000000 1 -0.474616 -3.016333 0.000000 1 1.825680 -2.023878 0.000000 6 -2.438930 1.153655 0.000000 1 -2.458973 -1.520140 0.000000 1 2.511794 1.692660 0.000000 7 -3.369050 1.851915 0.000000 1 0.129116 1.920076 0.000000 Low frequencies --- -10.9023 -8.9308 -0.0009 -0.0008 -0.0005 3.3674 Low frequencies --- 97.7847 131.6931 166.3872 1 2 3 A" A' A" Frequencies -- 97.7830 131.6927 166.3872 IR Inten -- 10.4373 10.6521 0.0499 4 5 6 A' A" A" Frequencies -- 232.6344 239.2297 400.0872 IR Inten -- 3.6649 5.4777 2.7179 7 8 9 A' A" A' Frequencies -- 418.6684 449.1124 466.8377 IR Inten -- 0.3017 4.3414 0.6826 10 11 12 A' A" A' Frequencies -- 561.3416 600.0909 673.6824 IR Inten -- 3.3402 2.1222 10.6450 13 14 15 A" A' A" Frequencies -- 698.8139 771.7977 823.2122 IR Inten -- 14.8234 33.3554 28.6385 16 17 18 ?A ?A A" Frequencies -- 920.1171 922.1269 959.1685 IR Inten -- 7.1314 11.7603 0.2826 19 20 21 A" A' A" Frequencies -- 1006.6199 1016.1584 1036.8462 IR Inten -- 0.0996 0.5058 0.4824 22 23 24 A' A' A' Frequencies -- 1117.6577 1177.8327 1201.7234 IR Inten -- 5.2922 36.1679 3.0267 25 26 27 A' A' A' Frequencies -- 1267.7124 1329.3614 1364.6550 IR Inten -- 44.3873 15.6486 3.3213 28 29 30 A' A' A' Frequencies -- 1424.4528 1476.9442 1528.9949 IR Inten -- 15.0514 3.0508 4.8085 31 32 33 A' A' A' Frequencies -- 1631.5069 1658.0153 1806.9418 IR Inten -- 20.3471 7.1824 228.4081 34 35 36 A' A' A' Frequencies -- 2351.6759 2924.2639 3202.8173 IR Inten -- 20.4702 112.5705 2.7091 37 38 39 A' A' A' Frequencies -- 3206.0158 3221.9629 3227.8566 IR Inten -- 2.9860 0.1659 6.2323 Zero-point correction= 0.108698 (Hartree/Particle) Thermal correction to Energy= 0.116785 Thermal correction to Enthalpy= 0.117729 Thermal correction to Gibbs Free Energy= 0.075415 ----------------------------------------------------------------------------- 8. m-cyanobenzaldehyde cis rotamer SCF Done: E(RB+HF-LYP) = -437.813694523 X Y Z 6 0.002697 -2.144008 0.000000 6 -1.204240 -1.443718 0.000000 6 -1.208616 -0.043615 0.000000 6 0.000000 0.661862 0.000000 6 1.210263 -0.039434 0.000000 6 1.208668 -1.448377 0.000000 6 -2.496131 0.696845 0.000000 8 -2.589458 1.907319 0.000000 1 0.005891 -3.229662 0.000000 1 -2.149352 -1.982205 0.000000 6 2.457754 0.670818 0.000000 1 2.153751 -1.981937 0.000000 1 -3.402268 0.052397 0.000000 7 3.472294 1.239139 0.000000 1 -0.020793 1.746640 0.000000 Low frequencies --- -0.0014 -0.0002 0.0004 1.2436 8.6101 9.2332 Low frequencies --- 121.5589 126.5900 139.8634 1 2 3 A" A' A" Frequencies -- 121.5573 126.5890 139.8627 IR Inten -- 3.7206 3.5734 1.7189 4 5 6 A' A" A" Frequencies -- 233.7840 243.0690 395.9816 IR Inten -- 9.6225 7.1390 0.9133 7 8 9 A' A" A' Frequencies -- 439.9856 456.6529 469.2277 IR Inten -- 0.2962 4.9055 0.4204 10 11 12 A' A" A' Frequencies -- 565.1998 601.4602 659.8461 IR Inten -- 1.7341 2.6713 20.9525 13 14 15 A" A' A" Frequencies -- 699.0277 739.2659 814.5018 IR Inten -- 15.4065 25.4215 28.3458 16 17 18 A" A" A' Frequencies -- 938.6333 952.4136 958.6173 IR Inten -- 1.3990 5.9862 15.1632 19 20 21 A" A' A" Frequencies -- 996.9278 1016.1973 1034.9993 IR Inten -- 0.0258 0.3155 0.5307 22 23 24 A' A' A' Frequencies -- 1124.8885 1161.2420 1205.4639 IR Inten -- 4.1688 45.3591 0.6134 25 26 27 A' A' A' Frequencies -- 1262.9829 1319.8356 1365.2295 IR Inten -- 35.8498 6.3985 2.0178 28 29 30 A' A' A' Frequencies -- 1432.3526 1480.5400 1524.2110 IR Inten -- 20.8385 8.0095 6.9751 31 32 33 A' A' A' Frequencies -- 1638.1456 1653.6589 1807.5944 IR Inten -- 2.0303 30.2013 204.8098 34 35 36 A' A' A' Frequencies -- 2354.1368 2924.6325 3188.3593 IR Inten -- 16.7468 127.9978 3.6529 37 38 39 A' A' A' Frequencies -- 3210.9972 3226.0094 3231.4473 IR Inten -- 6.5651 5.5880 1.8181 Zero-point correction= 0.108704 (Hartree/Particle) Thermal correction to Energy= 0.116781 Thermal correction to Enthalpy= 0.117725 Thermal correction to Gibbs Free Energy= 0.075414