Supporting Information
for
Economical Treatments of Relativistic Effects
and Electron Correlation in WH6
Supporting Information Table I.
Complete list of relative energies (kJ/mol) for WH6 isomers
Oh D3h C3v B
(staggered)
C5v C3v A (eclipsed)
RHF
1. LANL2[3s3p2d]:[2s1p] 546.8 109.3 48.5 5.5 0.0
2. SKBJ[4s4p3d]:[2s1p] 480.7 100.2 50.1 7.9 0.0
3. ecp-60-mwb[6s5p3d]:[2s1p] 441.8 87.5 56.8 4.7 0.0
4. ecp-60-mwb[6s5p3d1f]:[2s1p] 427.3 82.9 63.1 3.1 0.0
5. ecp-60-mwb[6s5p4d2f]:[3s2p] 409.8 78.7 71.9 1.0 0.0
6. ecp-60-mwb[6s5p4d3f]:[5s2p1d] 402.4 77.5 71.7 0.9 0.0
LANL2[3s3p2d]:[2s]a 527 105 46 8 0
LANL2[3s3p2d1f]:[4s2p]b 395.0 -- 72.0 2.5 0.0
LANL2[4s4p3d2f]:[4s2p1d]b 412.1 -- 71.1 2.5 0.0
EC60[4s3p3d]:[2s1p]d 455.2 94.6 54.4 5.9 0.0
Basis set D. [17s11p8d2f]:[3s2p]b 646.8 168.6 33.6 6.1 0.0
Basis set G. [19s17p11d4f]:[5s2p]b 613.2 162.1 33.6 6.3 0.0
BP iop(5/42=46) (G94) LANL1[2s2p2d]:[2s] 1056 277.5 7.5 11.3 0.0
BP86 (G94) LANL1[2s2p2d]:[2s] 1045 273.2 8.4 11.0 0.0
BP (Turbo) LANL1[2s2p2d]:[2s] 1051 275.2 8.4 11.8 0.0
ADF calcs, Becke-Perdew
II [Xe]4f14[2s1p2d]:[2s] 953.9 233.1 -0.4 9.3 0.0
IV [Xe]4f14[3s1p3d]:[3s1p] = IVa 989.6 249.4 8.4 7.5 0.0
IV [Kr]4d10[5s3p3d3f]:[3s1p] = IVb 881.0 228.9 7.2 8.1 0.0
II + relativistic core potential 811.1 195.2 12.7 5.9 0.0
II + relativistic core potential + scalar/pauli 817.2 190.2 28.5 0.8 0.0
IVa + relativistic core potential + scalar/pauli 823.1 199.3 30.8 0.8 0.0
IVb + relativistic core potential + scalar/pauli 609.1 133.6 48.7 -3.0 0.0
BP86
4. 659.4 153.4 35.5 0.8 0.0
5. 650.2 155.2 39.9 0.1 0.0
6. 645.4 154.6 39.9 0.0 0.0
ecp-60-mwb[6s5p3d]:[2s1p]c 661.9 153.2 34.9 1.9 0.0
BLYP
1. 756.4 158.5 40.2 0.8 0.0
2. 683.2 147.8 39.1 2.3 0.0
3. 633.0 136.6 45.5 -0.2 0.0
4. 622.7 134.8 47.1 -1.7 0.0
5. 611.7 135.6 50.9 -2.5 0.0
6. 606.9 134.8 50.8 -2.6 0.0
SVWN/EC60[4s3p3d]:[2s1p]d 761.5 197.5 10.0 10.0 0.0
BLYP/EC60[4s3p3d]:[2s1p]d 666.1 148.5 42.3 0.8 0.0
B3LYP
1. 731.0 156.3 38.7 2.3 0.0
4. 597.1 131.7 47.0 -0.6 0.0
5. 584.7 131.9 51.8 -1.7 0.0
6. 579.3 131.1 51.7 -1.7 0.0
ACM/EC60[4s3p3d]:[2s1p]d 673.2 164.8 28.0 6.3 0.0
MP2
1. 641.4 137.5 28.1 6.5 0.0
4. 614.9 147.6 26.0 2.9 0.0
5. 599.4 167.6 26.6 4.2 0.0
6. 605.4 175.2 22.8 5.0 0.0
LANL2[3s3p2d]:[2s]a 607 121 25 8 0
EC60[4s3p3d]:[2s1p]d 558.6 131.8 30.5 7.5 0.0
CCSD(T)
4. 579.3 124.6 37.9 0.9 0.0
5. 550.0 137.1 43.9 0.1 0.0
6. 554.7 143.9 40.4 0.7 0.0
Single point calculations
CCSD//RHF Basis set Db 802.9 -- 11.7 8.3 0.0
MP2//RHF Basis set Db 894.5 -- -9.9 13.4 0.0
MP2//RHF Basis set E [18s14p10d3f]:[4s2p]b 880.9 -- -13.1 14.1 0.0 MCPF+R//RHF Basis F [19s17p11d4f]:[4s2p]b 574.9 122.6 43.5 -1.7 0.0
CCSD//RHF LANL2[4s4p3d2f]:[4s2p1d]b 530.9 -- 48.5 -2.1 0.0
CCSD(T)//RHF LANL2[4s4p3d2f]:[4s2p1d]b 542.7 -- 45.2 -2.5 0.0
QCISD(T)//MP2 ? LANL2[3s3p2d]:[2s]a 594 109 33 4 0
MP2/III//MP2/IIe 618.4 132.8 26.3 4.4 0.0
MP2//B3LYP Basis set 4. 614.3 146.6 26.4 2.2 0.0
CCSD(T)//B3LYP Basis set 4. 579.5 124.5 38.0 0.7 0.0
CCSD(T)//MP2 Basis set 4. 577.7 123.1 38.4 0.0 0.0
D-K RHF/Basis set 7f 394.0 72.0 75.8 -1.7 0.0
MCPF/Basis set 7f 676.8 212.7 8.8 6.7 0.0
MCPF+R/Basis set 7f 444.2 126.8 43.2 -0.7 0.0
D-K MCPF/Basis set 7f 551.8 144.9 44.5 5.3 0.0
a S.K. Kang; H. Tang; T.A. Albright J. Am. Chem. Soc. 1993, 115, 1971-1981. b M. Shen; H.F. Schaefer; H. Partridge J. Chem. Phys. 1993, 98, 508-521. c M. Kaupp J.Am. Chem. Soc. 1996, 118, 3018-3024.
d N. Tanpipat; J. Baker J. Phys. Chem. 1996, 100, 19818-19823. e Frenking basis set III = LANL2[3s4p2d1f]:[2s].
Supporting Information Table II. Geometriesa ( and degree) and total energies (Hartree) for WH
1. LANL2[3s3p2d]:[2s1p] 1.7812
-70.210417
1.6983
-70.377038
86.4 1.7021
-70.400201
1.6272 119.8 61.6 1.7130
-70.416573
1.6558 113.7 1.6955
-70.418671
1.6407 112.8 63.5
2. SKBJ[4s4p3d]:[2s1p] 1.7917
-70.204311
1.7176
-70.349230
86.6 1.7197
-70.368331
1.6400 119.8 61.9 1.7382
-70.384390
1.6743 113.7 1.7171
-70.387409
1.6574 112.6 63.8
3. ecp-60-mwb[6s5p3d]:[2s1p] 1.7899
-69.518727
1.7215
-69.653691
86.5 1.7229
-69.665375
1.6448 119.9 61.7 1.7365
-69.685221
1.6783 113.4 1.7188
-89.687008
1.6625 111.9 64.2
4. ecp-60-mwb[6s5p3d1f]:[2s1p] 1.7829
-69.538881
1.7168
-69.670063
86.6 1.7191
-69.677578
1.6396 120.0 61.6 1.7321
-69.700431
1.6738 113.4 1.7147
-69.701629
5. ecp-60-mwb[6s5p4d2f]:[3s2p] 1.7912
86.9 1.7264
-69.691146
1.6429 120.0 60.9 1.7434
-69.718134
1.6785 113.3 1.7224
-69.718526
1.6609 111.4 64.3
6. ecp-60-mwb[6s5p4d3f]:[5s2p1d] 1.7886
-69.567639
1.7235
-69.691389
86.8 1.7261
-69.693593
1.6416 120.0 60.86 1.7432
-69.720565
1.6774 113.3 1.7218
-69.720915
1.6598 111.3 64.27
Basis set D. [17s11p8d2f]:[3s2p]b 1.816 1.732 86.4 1.712 1.635 118.4 60.6 1.749 1.673 115.9 1.720 1.651 116.0 61.3
Basis set G. [19s17p11d4f]:[5s2p]b 1.833 1.741 86.6 1.720 1.639 118.3 60.5 1.760 1.679 115.9 1.728 1.656 116.1 61.2
EC60[4s3p3d]:[2s1p]d 1.784 1.714 86.1 1.716 1.632 119.9 60.9 1.732 1.666 113.9 1.712 1.647 112.7 63.3
BP iop(5/42=46) (G94)
85.2 1.6889
-11.560306
1.6398 115.2 63.8 1.7417
-11.558871
1.6794 116.9 1.7119
-11.563175
1.6575 117.9 61.4
BP86 (G94) LANL1[2s2p2d]:[2s] 1.9891
-10.951877
1.7788
-11.245711
85.2 1.6932
-11.346542
1.6431 115.3 63.8 1.7458
-11.345579
1.6829 116.9 1.7162
-11.349759
1.6610 117.8 61.4
BP (Turbo) LANL1[2s2p2d]:[2s] 1.9854
-1.7779
-85.1 1.6928
-1.6427 115.4 63.7 1.7450
-1.6820 116.9 1.7152
10.948101 11.243394 11.345012 11.343723 11.348216
ADF calcs, Becke-Perdew
II [2s1p2d]:[2s] 1.9437
-0.589368
1.8055
-0.863923
85.3 1.7550
-0.952871
1.7155 117.1 63.2 1.7862
-0.949169
1.7423 116.4 1.7669
-0.952707
1.7291 116.7 62.2
IV [3s1p3d]:[3s1p] 1.9127
-0.598797
1.7895
-0.880734
85.0 1.7355
-0.972539
1.6946 116.5 62.2 1.7716
-0.972869
1.7237 116.8 1.7495
-0.975726
1.7063 117.2 61.0
IV [5s3p3d3f]:[3s1p] 1.8596
-0.676114
1.7572
-0.924514
84.14 1.7066
-1.008952
1.6677 116.1 61.86 1.7484
-1.008605
1.6957 116.6 1.7254
-1.011688
1.6787 117.4 60.98
II + relativistic core potential 1.9422
-0.659144
1.8251
-0.893704
86.4 1.7864
-0.963228
1.7369 117.6 62.7 1.8156
-0.965824
1.7690 115.8 1.7956
-0.968065
1.7539 115.8 62.5
IV [3s1p3d] + relativistic core
poten-tial
1.9087
-0.676253
1.8070
-0.917921
86.4 1.7635
-0.986593
1.7168 117.8 61.5 1.7966
-0.995309
1.7478 116.1 1.7745
-0.996253
1.7315 116.1 61.3
II + relativistic core potential +
scalar/pauli
1.8984
-0.657979
1.7787
-0.896826
87.8 1.7408
-0.958410
1.7020 118.6 62.9 1.7654
-0.968934
1.7232 115.1 1.7483
-0.969251
1.7132 114.5 63.4
IV [3s1p3d] + relativistic core
poten-tial + scalar/pauli
1.8614
-0.666675
1.7598
-0.904287
87.2 1.7208
-0.968436
1.6757 118.5 61.9 1.7473
-0.979879
1.7013 115.5 1.7286
-0.980183
1.6894 115.3 62.0
tential + scalar/pauli -1.159547 -1.340667 -1.372997 -1.392705 -1.391547
BP86
4. 1.8139
-70.449640
1.7354
-70.642362
86.22 1.7054
-70.687253
1.6606 118.8 62.17 1.7326
-70.700462
1.6870 114.8 1.7133
-70.700782
1.6737 114.4 62.74
5. 1.8186
-70.460403
1.7388
-70.648930
86.56 1.7063
-70.692836
1.6592 118.8 61.64 1.7393
-70.708023
1.6879 115.0 1.7165
-70.708051
1.6728 114.7 62.28
6. 1.8163
-70.463775
1.7380
-70.650733
86.51 1.7055
-70.694409
1.6587 118.8 61.53 1.7387
-70.709606
1.6870 115.0 1.7155
-70.709613
1.6724 114.6 62.28
ecp-60-mwb[6s5p3d]:[2s1p]c 1.716 1.676 114.5 62.6
BLYP
1. 1.8205
-70.926389
1.7241
-71.154099
85.9 1.7006
-71.199158
1.6556 119.1 62.4 1.7203
-71.214188
1.6782 114.6 1.7037
-71.214481
2. 1.8193
85.9 1.7109
-71.167400
1.6628 119.0 62.4 1.7351
-71.181428
1.6892 114.7 1.7165
-71.182290
1.6761 113.9 63.2
3. 1.8190
86.2 1.7172
-70.519575
1.6696 119.2 62.2 1.7399
-70.536962
1.6956 114.5 1.7223
-70.536886
1.6833 113.6 63.4
4. 1.8143
86.4 1.7156
-70.522852
1.6668 119.3 62.2 1.7382
-70.541468
1.6926 114.4 1.7201
-70.540802
1.6793 113.6 63.4
5. 1.8203
86.7 1.7167
-70.527534
1.6662 119.3 61.9 1.7443
-70.547866
1.6927 114.5 1.7241
-70.546917
1.6796 113.8 63.2
6. 1.8186
86.6 1.7168
-70.529095
1.6656 119.3 61.8 1.7430
-70.549397
1.6926 114.5 1.7239
-70.548425
1.6788 113.7 63.1
SVWN/EC60[4s3p3d]:[2s1p]d 1.817 1.730 85.0 1.686 1.643 116.9 61.7 1.726 1.672 116.0 1.701 1.655 116.7 60.7
B3LYP
86.0 1.6912
-71.202934
1.6426 119.1 62.1 1.7117
-71.216815
1.6659 114.7 1.6936
-71.217686
1.6534 114.2 62.9
4. 1.8029
86.4 1.7062
-70.511384
1.6529 119.3 62.0 1.7298
-70.529519
1.6807 114.4 1.7112
-70.529276
1.6667 113.6 63.3
5. 1.8084
86.7 1.7088
-70.517165
1.6529 119.4 61.5 1.7379
-70.537522
1.6828 114.5 1.7155
-70.536893
1.6673 113.8 62.9
6. 1.8068
86.7 1.7080
-70.518835
1.6522 119.4 61.5 1.7363
-70.539170
1.6819 114.5 1.7147
-70.538509
1.6667 113.8 62.9
ACM/EC60[4s3p3d]:[2s1p]d 1.804 1.722 85.4 1.689 1.636 118.2 61.5 1.722 1.666 115.4 1.699 1.649 115.5 61.6
MP2
LANL2[3s4p2d]:[2s] (Frenking II) 1.8158
-1.7367
-85.6 1.7251
-1.6806 119.6 62.9 1.7538
-1.7029 113.4 1.7284
70.440944 70.610466 70.638463 70.648927 70.651666
85.7 1.6760
-70.663095
1.6216 119.4 61.0 1.7033
-70.671328
1.6443 114.3 1.6786
-70.673801
1.6304 113.5 61.9
4. 1.7800
86.0 1.6770
-70.115904
1.6334 119.0 60.6 1.7104
-70.124687
1.6585 114.8 1.6861
-70.125802
1.6447 114.4 61.7
5. 1.7909
86.7 1.6871
-70.249846
1.6491 117.7 60.8 1.7351
-70.258366
1.6760 115.6 1.7046
-70.259972
1.6606 116.0 60.2
6. 1.7841
86.8 1.6764
-70.279718
1.6371 117.3 60.7 1.7296
-70.286512
1.6656 115.8 1.6959
-70.288405
1.6493 116.3 60.1
EC60[4s3p3d]:[2s1p]d 1.777 1.708 85.4 1.684 1.623 119.0 59.5 1.718 1.654 114.8 1.691 1.635 114.5 60.3
CCSD(T)
4. 1.7862
-1.7151
-85.8 1.6941
-1.6427 119.6 61.2 1.7166
-1.6690 114.0 1.6976
69.933433 70.106621 70.139642 70.153725 70.154080
86.5 1.7080
-70.275187
1.6566 119.1 61.0 1.7429
-70.291849
1.6863 114.6 1.7176
-70.291899
1.6704 114.3 62.0
6. 1.7906
86.6 1.6966
-70.302946
1.6428 118.87 60.92 1.7365
-70.318079
1.6750 114.8 1.7083
-70.318329
1.6577 114.62 61.72
Single point calculations
MP2/III//MP2/IIe
680257 854022 902708 913402 915439
RHF+R/Basis set 7f -16035.
393745
-16035.
511965
-16035.
511634
-16035.
540165
D-K RHF/Basis set 7f -16043.
684750
-16043.
807399
-16043.
805954
-16043.
835489
-16043.
834828
MCPF/Basis set 7f -15291.
203882
-15291.
380563
-15291.
458112
-15291.
458968
-15291.
461501
MCPF+R/Basis set 7f -16035.
905990
-16036.
026830
-16036.
058619
-16036.
075362
-16036.
075084
D-K MCPF/Basis set 7f -16044.
027567
-16044.
182433
-16044.
220637
-16044.
235570
-16044.
237586
Use Word 6.0c or later to
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b M. Shen; H.F. Schaefer; H. Partridge J. Chem. Phys. 1993, 98, 508.
c M. Kaupp J.Am. Chem. Soc. 1996, 118, 3018-3024.
d N. Tanpipat; J. Baker J. Phys. Chem. 1996, 100, 19818-19823.
e Frenking basis set III = LANL2[3s4p2d1f]:[2s].
Supporting Information Table III. Vibrational frequencies (cm-1) and infrared intensities (km/mole) for WH6 isomers calculated at MP2/Basis set 4
Oh D3h C3v B
(stag-gered)
C5v C3v A
(eclipsed
)
Freq Intensity Freq Intensity Freq Intensity Freq Intensity Freq Intensity
-2419 0 -1194 311 534 0 698 0 656 23
-2419 0 -458 0 692 103 698 0 656 23
-2419 0 -458 0 778 0 703 22 745 9
-2004 2166 479 0 778 0 703 22 799 0
-2004 2166 479 0 889 34 865 127 860 59
-2004 2166 890 2 889 34 865 127 860 59
687 0 890 2 1054 88 967 2 909 42
687 0 959 0 1073 146 1002 0 909 42
687 0 1084 0 1073 146 1002 0 1093 142
1827 561 2013 0 2073 39 2020 281 2060 207
1827 561 2013 0 2080 212 2114 52 2060 207
1827 561 2025 222 2080 212 2115 0 2071 89
2040 0 2025 222 2165 21 2115 0 2146 60
2040 0 2026 122 2200 32 2131 194 2165 64
