An Examination of Density Functionals on Aldol, Mannich, Andα-Aminoxylation Reaction Enthalpies
Supporting Information
An Examination of Density Functionals on Aldol, Mannich, andα-Aminoxylation Reaction Enthalpies
Raman K. Singh, Takao Tsuneda and Kimihiko Hirao
Advanced Science Institute, RIKEN, Wako, Saitama 351-0198, Japan
CREST, Japan Science and Technology Agency (JST), Tokyo 113-8656, Japan
ContentsPage
Figure 1: Basis Set effectsS2
Table S1: aug-cc-pVTZ Reaction EnthalpiesS3
Table S2: cc-pVTZ Reaction EnthalpiesS6
TableS3: cc-pVDZ Reaction EnthalpiesS9
Figure 1: Basis set effects on the reaction enthalpies of reactions 1-9.
Table S1:Enthalpies (0K, hartree) from BOP, LC-BOP, LCgau-BOP,LC-ωPBE, CAM-B3LYPand B3LYPusing aug-cc-pVTZ basis set.
Systems / BOP / LC-BOP / LCgau-BOP / LC-ωPBE / CAM-B3LYP / B3LYP1 / acetaldehyde / -153.783298 / -153.436508 / -153.957306 / -153.735902 / -153.765036 / -153.841222
2 / formaldehyde / -114.495425 / -114.249123 / -114.641969 / -114.446502 / -114.474934 / -114.525645
3 / 3-hydroxypropanal / -268.281364 / -267.711848 / -268.623856 / -268.209967 / -268.262026 / -268.382294
4 / 3-hydroxybutanal / -307.558179 / -306.890074 / -307.930424 / -307.490379 / -307.542940 / -307.687876
5 / propanal / -193.055420 / -192.608754 / -193.257517 / -193.010539 / -193.039888 / -193.141296
6 / 3-hydroxy-2-methylpropanal / -307.552507 / -306.884032 / -307.924313 / -307.484839 / -307.536895 / -307.681958
7 / acetone / -193.066443 / -192.620936 / -193.269830 / -193.022686 / -193.051966 / -193.153011
8 / 4-hydroxy-4-methylpentan-2-one / -386.114656 / -385.250974 / -386.547658 / -386.055961 / -386.108481 / -386.302305
9 / methanimine / -94.594549 / -94.359733 / -94.693612 / -94.560445 / -94.578485 / -94.632232
10 / 3-aminopropanal / -248.384498 / -247.826663 / -248.679572 / -248.329638 / -248.369244 / -248.492576
11 / Ethanamine / -135.061629 / -134.735951 / -135.192832 / -135.053839 / -135.059880 / -135.142334
12 / 3-aminobutanal / -287.658822 / -287.002279 / -287.983614 / -287.607683 / -287.647596 / -287.795636
13 / 3-amino-2-methylpropanal / -287.656040 / -286.999224 / -287.980326 / -287.604757 / -287.644412 / -287.792582
14 / nitrosylhydride / -130.494451 / -130.230520 / -130.702648 / -130.430528 / -130.465146 / -130.513703
15 / 2-(aminooxy)acetaldehyde / -284.289042 / -283.699192 / -284.689933 / -284.196638 / -284.260249 / -284.379159
16 / 2-(aninooxy)propanal / -323.565439 / -322.876836 / -323.995616 / -323.476380 / -323.540282 / -323.683965
17 / methane / -40.462553 / -40.350124 / -40.474509 / -40.464143 / -40.459344 / -40.493881
18 / methanol / -115.680502 / -115.442395 / -115.830211 / -115.653441 / -115.671292 / -115.725717
19 / ethane / -79.731851 / -79.517967 / -79.770400 / -79.734565 / -79.730125 / -79.790398
20 / methanamine / -95.787028 / -95.561422 / -95.890013 / -95.777009 / -95.782465 / -95.839690
21 / water / -76.426513 / -76.292110 / -76.550853 / -76.401298 / -76.416666 / -76.444960
22 / hydroxylamine / -131.703465 / -131.448721 / -131.914437 / -131.660372 / -131.686983 / -131.739270
23 / ethanol / -154.957443 / -154.619241 / -155.135217 / -154.932421 / -154.950854 / -155.030488
24 / Propane / -119.003597 / -118.689596 / -119.070147 / -119.008578 / -119.004477 / -119.090045
25 / propan-2-ol / -194.233668 / -193.796894 / -194.441232 / -194.212359 / -194.231125 / -194.335464
26 / o-methylhydroxylamine / -133.878180 / -170.607717 / -171.202412 / -170.920448 / -170.950075 / -171.028087
27 / ethanimine / -133.542918 / -134.004906 / -133.845939 / -133.864507 / -133.943736
28 / N,N-dimethylethanamine / -212.401762 / -211.866865 / -211.903754 / -212.372908 / -212.394717 / -212.524445
29 / methanimine / -94.594549 / -94.359733 / -94.693612 / -94.560445 / -94.578485 / -94.632232
30 / 4-hydroxybutan-2-one / -307.565258 / -306.897219 / -307.937345 / -307.497653 / -307.549836 / -307.694889
31 / Isobutyraldehyde / -232.327055 / -231.781218 / -232.558149 / -232.285486 / -232.314964 / -232.441260
32 / 2-hydroxyethanal / -229.001843 / -228.529882 / -229.314237 / -228.926266 / -228.978185 / -229.074038
33 / o-ethylhydroxylamine / -210.241550 / -209.784399 / -210.506927 / -210.199061 / -210.229117 / -210.332223
34 / propanamine / -174.331090 / -173.905502 / -174.490633 / -174.326116 / -174.332349 / -174.439989
Table S1: Enthalpies (0K, hartree) from BMK and M06-2x using aug-cc-pVTZ basis set.
Systems / BMK / M06-2x1 / acetaldehyde / -153.739340 / -153.764882
2 / formaldehyde / -114.456878 / -114.471878
3 / 3-hydroxypropanal / -268.217206 / -268.264527
4 / 3-hydroxybutanal / -307.491470 / -307.549895
5 / propanal / -193.007601 / -193.044265
6 / 3-hydroxy-2-methylpropanal / -307.486056 / -307.545063
7 / acetone / -193.020264 / -193.055566
8 / 4-hydroxy-4-methylpentan-2-one / -386.044275 / -386.126186
9 / methanimine / -94.561967 / -94.581015
10 / 3-aminopropanal / -248.328286 / -248.375816
11 / ethyanamine / -135.033239 / -135.062768
12 / 3-aminobutanal / -287.600028 / -287.659216
13 / 3-amino-2-methylpropanal / -287.597199 / -287.656428
14 / nitrosylhydride / -130.439065 / -130.459131
15 / 2-(aminooxy)acetaldehyde / -284.211925 / -284.258085
16 / 2-(aninooxy)propanal / -323.485933 / -323.542618
17 / methane / -40.448792 / -40.456662
18 / methanol / -115.647629 / -115.665988
19 / ethane / -79.712228 / -79.731413
20 / methanamine / -95.762389 / -95.781276
21 / water / -76.399948 / -76.408536
22 / hydroxylamine / -131.659510 / -131.677900
23 / ethanol / -154.920397 / -154.949430
24 / propane / -118.980670 / -119.009420
25 / propan-2-ol / -194.193599 / -194.234348
26 / o-methylhydroxylamine / -170.916055 / -170.944282
27 / ethanimine / -133.840581 / -133.870207
28 / N,N-dimethylethanamine / -212.356555 / -212.410887
29 / methanimine / -94.561967 / -94.581015
30 / 4-hydroxybutan-2-one / -307.497617 / -307.556595
31 / Isobutyraldehyde / -232.276765 / -232.324567
32 / 2-hydroxyethanal / -228.940038 / -228.975424
33 / o-ethylhydroxylamine / -210.188656 / -210.227597
34 / propanamine / -174.298547 / -174.339549
Table S2: Enthalpies (0K, hartree) from BOP, LC-BOP, LCgau-BOP,LC-ωPBE, CAM-B3LYP and B3LYP using cc-pVTZ basis set.
Systems / BOP / LC-BOP / LCgau-BOP / LC-ωPBE / CAM-B3LYP / B3LYP1 / acetaldehyde / -153.780354 / -153.433611 / -153.954183 / -153.732870 / -153.761955 / -153.838289
2 / formaldehyde / -114.492599 / -114.246365 / -114.639007 / -114.443716 / -114.472035 / -114.522877
3 / 3-hydroxypropanal / -268.275189 / -267.706131 / -268.617924 / -268.204124 / -268.256040 / -268.376506
4 / 3-hydroxybutanal / -307.552165 / -306.884582 / -307.924507 / -307.484444 / -307.536924 / -307.682063
5 / propanal / -193.052648 / -192.606135 / -193.254588 / -193.007607 / -193.036966 / -193.138493
6 / 3-hydroxy-2-methylpropanal / -307.546697 / -306.878692 / -324.389107 / -307.479107 / -307.531121 / -307.676388
7 / acetone / -193.063466 / -192.617977 / -193.266644 / -193.019464 / -193.048725 / -193.149991
8 / 4-hydroxy-4-methylpentan-2-one / -386.108940 / -385.245990 / -385.245990 / -386.049764 / -386.102358 / -386.296402
9 / methanimine / -94.591589 / -94.356157 / -94.691056 / -94.558047 / -94.575790 / -94.629603
10 / 3-aminopropanal / -248.378447 / -247.820742 / -248.674477 / -248.324624 / -248.363965 / -248.487438
11 / Ethanamine / -135.057664 / -134.732101 / -135.189525 / -135.050659 / -135.056351 / -135.138862
12 / 3-aminobutanal / -287.652972 / -286.996746 / -287.978450 / -287.602493 / -287.642221 / -287.790411
13 / 3-amino-2-methylpropanal / -287.649933 / -286.993352 / -287.975089 / -287.599469 / -287.638945 / -287.787257
14 / nitrosylhydride / -130.490023 / -130.226582 / -130.698492 / -130.426637 / -130.460958 / -130.509636
15 / 2-(aminooxy)acetaldehyde / -284.281569 / -283.692078 / -284.683284 / -284.190087 / -284.253425 / -284.372522
16 / 2-(aninooxy)propanal / -323.558023 / -322.869832 / -323.988923 / -323.469675 / -323.533382 / -323.677254
17 / methane / -40.461606 / -40.349667 / -40.474241 / -40.463893 / -40.459104 / -40.493653
18 / methanol / -115.675770 / -115.438212 / -115.825688 / -115.649192 / -115.666671 / -115.721184
19 / ethane / -79.731676 / -79.517728 / -79.769895 / -79.734043 / -79.729635 / -79.789955
20 / methanamine / -95.782887 / -95.557359 / -95.886756 / -95.773950 / -95.778960 / -95.836209
21 / water / -76.419549 / -76.286338 / -76.544556 / -76.395448 / -76.410168 / -76.438561
22 / hydroxylamine / -131.696393 / -131.442440 / -131.908431 / -131.654689 / -131.680705 / -131.733059
23 / ethanol / -154.953255 / -154.615393 / -155.130989 / -154.928345 / -154.946563 / -155.026329
24 / propane / -119.003240 / -118.689200 / -119.042381 / -119.007738 / -119.003724 / -119.089333
25 / propan-2-ol / -194.229769 / -193.793346 / -194.437121 / -194.208277 / -194.226941 / -194.331434
26 / o-methylhydroxylamine / -170.959564 / -170.602442 / -171.197553 / -170.915734 / -170.945007 / -171.023103
27 / ethanimine / -133.874857 / -133.539065 / -134.002092 / -133.843247 / -133.861559 / -133.940871
28 / N,N-dimethylethanamine / -212.398630 / -211.863993 / -212.580604 / -212.370182 / -212.391853 / -212.521595
29 / methanimine / -94.591589 / -94.356157 / -94.691056 / -94.558047 / -94.575790 / -94.629603
30 / 4-hydroxybutan-2-one / -307.559025 / -306.891385 / -307.931197 / -307.491525 / -307.543616 / -307.688898
31 / Isobutyraldehyde / -232.324216 / -231.778641 / -232.555052 / -232.282256 / -232.311818 / -232.438243
32 / 2-hydroxyethanal / -228.995054 / -228.523619 / -229.307699 / -228.919954 / -228.971553 / -229.067609
33 / o-ethylhydroxylamine / -210.236236 / -209.779414 / -210.502316 / -210.194490 / -210.224305 / -210.327499
34 / propanamine / -174.326797 / -173.901233 / -174.487111 / -174.322649 / -174.328583 / -174.436278
Table S2: Enthalpies (0K, hartree) from BMK and M06-2x using cc-pVTZ basis set.
Systems / BMK / M06-2x1 / acetaldehyde / -153.736388 / -153.762175
2 / formaldehyde / -114.454443 / -114.469499
3 / 3-hydroxypropanal / -268.211797 / -268.259382
4 / 3-hydroxybutanal / -307.486000 / -307.544505
5 / propanal / -193.004638 / -193.041632
6 / 3-hydroxy-2-methylpropanal / -307.480773 / -307.539774
7 / acetone / -193.016573 / -193.052519
8 / 4-hydroxy-4-methylpentan-2-one / -386.037676 / -386.120438
9 / methanimine / -94.559663 / -94.578742
10 / 3-aminopropanal / -248.323835 / -248.371107
11 / ethanamine / -135.029589 / -135.059570
12 / 3-aminobutanal / -287.595053 / -287.654320
13 / 3-amino-2-methylpropanal / -287.591955 / -287.651424
14 / nitrosylhydride / -130.436142 / -130.455849
15 / 2-(aminooxy)acetaldehyde / -284.206212 / -284.252246
16 / 2-(aninooxy)propanal / -323.480452 / -323.536602
17 / methane / -40.448120 / -40.456338
18 / methanol / -115.643756 / -115.662276
19 / ethane / -79.711202 / -79.730783
20 / methanamine / -95.759236 / -95.778285
21 / water / -76.395331 / -76.403666
22 / hydroxylamine / -131.655033 / -131.673002
23 / ethanol / -154.916321 / -154.945729
24 / propane / -118.978742 / -119.008385
25 / propan-2-ol / -194.189394 / -194.230578
26 / o-methylhydroxylamine / -170.911695 / -170.940084
27 / ethanimine / -133.837722 / -133.867571
28 / N,N-dimethylethanamine / -212.352825 / -212.407965
29 / methanimine / -94.559663 / -94.578742
30 / 4-hydroxybutan-2-one / -307.491973 / -307.551063
31 / Isobutyraldehyde / -232.273177 / -232.321523
32 / 2-hydroxyethanal / -228.934583 / -228.969904
33 / o-ethylhydroxylamine / -210.184198 / -210.223487
34 / propanamine / -174.294428 / -174.336084
Table S3: Enthalpies (0K, hartree) from BOP, LC-BOP, LCgau-BOP,LC-ωPBE, CAM-B3LYP and B3LYP using cc-pVDZ basis set.
Systems / BOP / LC-BOP / LCgau-BOP / LC-ωPBE / CAM-B3LYP / B3LYP1 / acetaldehyde / -153.724867 / -153.376873 / -153.901168 / -153.682178 / -153.705854 / -153.783124
2 / formaldehyde / -114.454747 / -114.202120 / -114.598884 / -114.404784 / -114.429647 / -114.481284
3 / 3-hydroxypropanal / -268.182738 / -267.610999 / -268.527356 / -268.116376 / -268.160811 / -268.282844
4 / 3-hydroxybutanal / -307.446319 / -306.776073 / -307.821439 / -307.385436 / -307.428537 / -307.575451
5 / propanal / -192.984196 / -192.536615 / -193.189567 / -192.946057 / -192.968063 / -193.070626
6 / 3-hydroxy-2-methylpropanal / -307.441370 / -306.770884 / -307.815974 / -307.380518 / -307.423093 / -307.570069
7 / acetone / -192.994233 / -192.547751 / -193.200890 / -192.957202 / -192.979092 / -193.081432
8 / 4-hydroxy-4-methylpentan-2-one / -385.976768 / -385.110847 / -386.413945 / -385.928556 / -385.967971 / -386.164225
9 / methanimine / -94.555823 / -94.320980 / -94.656683 / -94.525811 / -94.539230 / -94.593607
10 / 3-aminopropanal / -248.292494 / -247.733208 / -248.590568 / -248.244420 / -248.275476 / -248.400432
11 / Ethanamine / -135.003014 / -134.679242 / -135.137836 / -135.002242 / -135.001053 / -135.084005
12 / 3-aminobutanal / -287.553724 / -286.895837 / -287.882040 / -287.511018 / -287.540585 / -287.690441
13 / 3-amino-2-methylpropanal / -287.550628 / -286.892661 / -287.878579 / -287.507929 / -287.537177 / -287.687114
14 / nitrosylhydride / -130.446820 / -130.180932 / -130.656021 / -130.384659 / -130.416693 / -130.466414
15 / 2-(aminooxy)acetaldehyde / -284.185401 / -283.593080 / -284.588098 / -284.097324 / -284.153849 / -284.274659
16 / 2-(aninooxy)propanal / -323.448230 / -322.757314 / -323.880898 / -323.365346 / -323.420248 / -323.565981
17 / methane / -40.439901 / -40.329709 / -40.454863 / -40.446398 / -40.437650 / -40.472011
18 / methanol / -115.626934 / -115.389784 / -115.779144 / -115.603853 / -115.617104 / -115.672036
19 / ethane / -79.695728 / -79.484137 / -79.738082 / -79.705208 / -79.694939 / -79.755218
20 / methanamine / -95.741699 / -95.518072 / -95.847686 / -95.736971 / -95.736998 / -95.794501
21 / water / -76.379331 / -76.246356 / -76.507571 / -76.358009 / -76.370667 / -76.399520
22 / hydroxylamine / -131.642932 / -131.389674 / -131.856373 / -131.602903 / -131.625724 / -131.678675
23 / ethanol / -154.891513 / -154.554215 / -155.072277 / -154.871977 / -154.884151 / -154.964530
24 / Propane / -118.953816 / -118.642052 / -119.024894 / -118.967340 / -118.955666 / -119.041436
25 / propan-2-ol / -194.155460 / -193.719246 / -194.366187 / -194.140890 / -194.151739 / -194.257099
26 / o-methylhydroxylamine / -170.894874 / -170.538186 / -171.135119 / -170.855209 / -170.879177 / -170.957956
27 / ethanimine / -133.825404 / -133.490219 / -133.954642 / -133.799096 / -133.811089 / -133.891127
28 / N,N-dimethylethanamine / -212.322670 / -211.788131 / -212.508060 / -212.303504 / -212.314972 / -212.445625
29 / methanimine / -94.555823 / -94.320980 / -94.656683 / -94.525811 / -94.539230 / -94.593607
30 / 4-hydroxybutan-2-one / -307.452911 / -306.782871 / -307.828057 / -307.392339 / -307.435046 / -307.582054
31 / Isobutyraldehyde / -232.242562 / -231.695746 / -232.477320 / -232.209234 / -232.229552 / -232.357227
32 / 2-hydroxyethanal / -228.914100 / -228.439938 / -229.227870 / -228.841799 / -228.887691 / -228.985208
33 / o-ethylhydroxylamine / -210.158950 / -209.702620 / -210.427640 / -210.122896 / -210.145508 / -210.249558
34 / propanamine / -174.259078 / -173.835100 / -174.422489 / -174.262483 / -174.259598 / -174.367919
Table S3: Enthalpies (0K, hartree) from BMK and M06-2x using cc-pVDZ basis set.
Systems / BMK / M06-2x1 / acetaldehyde / -153.688349 / -153.711636
2 / formaldehyde / -114.418667 / -114.431472
3 / 3-hydroxypropanal / -268.130653 / -268.172627
4 / 3-hydroxybutanal / -307.392174 / -307.445751
5 / propanal / -192.944835 / -192.979676
6 / 3-hydroxy-2-methylpropanal / -307.386795 / -307.441375
7 / acetone / -192.956203 / -192.989811
8 / 4-hydroxy-4-methylpentan-2-one / -385.919518 / -385.998013
9 / methanimine / -94.527919 / -94.546565
10 / 3-aminopropanal / -248.247309 / -248.291318
11 / Ethanamine / -134.980655 / -135.008845
12 / 3-aminobutanal / -287.506476 / -287.562637
13 / 3-amino-2-methylpropanal / -287.503569 / -287.559554
14 / nitrosylhydride / -130.400100 / -130.416219
15 / 2-(aminooxy)acetaldehyde / -284.121449 / -284.161655
16 / 2-(aninooxy)propanal / -323.382778 / -323.433722
17 / methane / -40.428558 / -40.436275
18 / methanol / -115.601358 / -115.616168
19 / ethane / -79.679360 / -79.698805
20 / methanamine / -95.722640 / -95.739654
21 / water / -76.363010 / -76.367270
22 / hydroxylamine / -131.609635 / -131.622417
23 / ethanol / -154.862021 / -154.887810
24 / propane / -118.934473 / -118.964295
25 / propan-2-ol / -194.123223 / -194.161059
26 / o-methylhydroxylamine / -170.855337 / -170.879155
27 / ethanimine / -133.793366 / -133.822806
28 / N,N-dimethylethanamine / -212.283607 / -212.338843
29 / methanimine / -94.527919 / -94.546565
30 / 4-hydroxybutan-2-one / -307.399034 / -307.451919
31 / Isobutyraldehyde / -232.200868 / -232.247403
32 / 2-hydroxyethanal / -228.863545 / -228.893920
33 / o-ethylhydroxylamine / -210.115634 / -210.151036
34 / propanamine / -174.233041 / -174.272725
S1