suppmat1604.doc 77KB Jun 05 2011 09:30:47 PM
Supporting Information
for
Economical Treatments of Relativistic Effects
and Electron Correlation in WH6
Roland H. Hertwig, Wolfram Koch and Brian F. Yates
Supporting Information Table I.
Complete list of relative energies (kJ/mol) for WH 6 isomers
Oh
D3h
C3v B
C5v
(staggered)
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
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
1056
277.5
7.5
11.3
0.0
BP iop(5/42=46) (G94)
LANL1[2s2p2d]:[2s]
105
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
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
IVa + relativistic core potential
840.2
205.7
25.4
2.5
0.0
ADF calcs, Becke-Perdew
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
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
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
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
553.3
108.2
34.7
7.2
0.0
BP86
BLYP
B3LYP
MP2
LANL2[3s4p2d]:[2s] (Frenking II)
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
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
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
RHF/Basis set 7f
617.5
161.3
33.4
5.3
0.0
CCSD(T)
Single point calculations
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].
f All-electron basis set 7 = [18s17p12d5f]:[3s2p]. Geometries were optimized at CCSD(T)/Basis set 6.
Supporting Information Table II. Geometries a ( and degree) and total energies (Hartree) for WH 6 isomers
Oh
D3h
C3v B
C5v
C3v A
(staggered)
(eclipsed)
r2
1
2
r
r
r1
r1
r2
r1
1.7812
1.6983
86.4
1.7021
-
-
-
-
-
70.210417
70.377038
70.400201
70.416573
70.418671
1.7917
1.7176
-
-
-
-
-
70.204311
70.349230
70.368331
70.384390
70.387409
1.7899
1.7215
-
-
-
-
-
69.518727
69.653691
69.665375
69.685221
89.687008
1.7829
1.7168
-
-
-
-
-
69.538881
69.670063
69.677578
69.700431
69.701629
r2
1
2
RHF
1. LANL2[3s3p2d]:[2s1p]
2. SKBJ[4s4p3d]:[2s1p]
3. ecp-60-mwb[6s5p3d]:[2s1p]
4. ecp-60-mwb[6s5p3d1f]:[2s1p]
86.6
86.5
86.6
1.7197
1.7229
1.7191
1.6272
1.6400
1.6448
1.6396
119.8
119.8
119.9
120.0
61.6
61.9
61.7
61.6
1.7130
1.7382
1.7365
1.7321
1.6558
1.6743
1.6783
1.6738
113.7
113.7
113.4
113.4
1.6955
1.7171
1.7188
1.7147
1.6407
112.8
63.5
1.6574
112.6
63.8
1.6625
111.9
64.2
1.6574
111.5
64.4
5. ecp-60-mwb[6s5p4d2f]:[3s2p]
1.7912
1.7247
-
-
-
-
-
69.562439
69.688563
69.691146
69.718134
69.718526
1.7886
1.7235
-
-
-
-
-
69.567639
69.691389
69.693593
69.720565
69.720915
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
Basis set G. [19s17p11d4f]:[5s2p] b
1.833
1.741
86.6
1.720
1.639
118.3
60.5
1.760
1.679
EC60[4s3p3d]:[2s1p]d
1.784
1.714
86.1
1.716
1.632
119.9
60.9
1.732
BP iop(5/42=46) (G94)
1.9853
1.7754
85.2
1.6889
1.6398
115.2
63.8
1.7417
LANL1[2s2p2d]:[2s]
-
-
-
-
-
11.160838
11.457474
11.560306
11.558871
11.563175
1.9891
1.7788
-
-
-
-
-
10.951877
11.245711
11.346542
11.345579
11.349759
1.9854
1.7779
-
-
6. ecp-60-mwb[6s5p4d3f]:[5s2p1d]
BP86 (G94)
BP (Turbo)
LANL1[2s2p2d]:[2s]
LANL1[2s2p2d]:[2s]
86.9
86.8
85.2
85.1
1.7264
1.7261
1.6932
1.6928
-
1.6429
1.6416
1.6431
1.6427
120.0
120.0
115.3
115.4
60.9
60.86
63.8
63.7
1.7434
1.7432
1.7458
1.7450
-
1.6785
1.6609
111.4
64.3
1.6598
111.3
64.27
1.720
1.651
116.0
61.3
115.9
1.728
1.656
116.1
61.2
1.666
113.9
1.712
1.647
112.7
63.3
1.6794
116.9
1.7119
1.6575
117.9
61.4
1.6610
117.8
61.4
1.6603
117.8
61.4
1.6774
1.6829
1.6820
113.3
113.3
116.9
116.9
1.7224
1.7218
1.7162
1.7152
-
10.948101
11.243394
1.9437
1.8055
-0.589368
-0.863923
1.9127
1.7895
-0.598797
-0.880734
1.8596
1.7572
-0.676114
-0.924514
1.9422
1.8251
-0.659144
-0.893704
1.9087
1.8070
-0.676253
-0.917921
1.8984
1.7787
-0.657979
-0.896826
1.8614
1.7598
-0.666675
-0.904287
1.7801
1.7127
11.345012
11.343723
11.348216
ADF calcs, Becke-Perdew
II [2s1p2d]:[2s]
IV [3s1p3d]:[3s1p]
IV [5s3p3d3f]:[3s1p]
II + relativistic core potential
IV [3s1p3d] + relativistic core potential
II + relativistic core potential +
scalar/pauli
IV [3s1p3d] + relativistic core potential + scalar/pauli
IV [5s3p3d3f] + relativistic core po-
85.3
1.7550
1.7155
117.1
63.2
-0.952871
85.0
1.7355
1.7066
1.6946
116.5
62.2
1.7864
1.6677
116.1
61.86
1.7635
1.7369
117.6
62.7
1.7408
1.7168
117.8
61.5
1.7208
1.7020
118.6
62.9
1.6875
1.7484
1.8156
1.7966
1.7654
1.6757
118.5
61.9
1.7473
1.6957
116.6
119.0
61.44
1.7077
116.7
62.2
1.7495
1.7063
117.2
61.0
1.7254
1.6787
117.4
60.98
1.7539
115.8
62.5
1.7315
116.1
61.3
1.7132
114.5
63.4
1.6894
115.3
62.0
1.6584
113.7
62.54
-1.011688
1.7690
115.8
1.7956
-0.968065
1.7478
116.1
1.7745
-0.996253
1.7232
115.1
1.7483
-0.969251
1.7013
115.5
-0.979879
1.6435
1.7291
-0.975726
-0.968934
-0.968436
85.62
116.8
-0.995309
-0.958410
87.2
1.7237
-0.965824
-0.986593
87.8
1.7716
1.7669
-0.952707
-1.008605
-0.963228
86.4
116.4
-0.972869
-1.008952
86.4
1.7423
-0.949169
-0.972539
84.14
1.7862
1.7286
-0.980183
1.6694
114.4
1.6929
tential + scalar/pauli
-1.159547
-1.340667
-1.372997
-1.392705
-1.391547
1.8139
1.7354
-
-
-
-
-
70.449640
70.642362
70.687253
70.700462
70.700782
1.8186
1.7388
-
-
-
-
-
70.460403
70.648930
70.692836
70.708023
70.708051
1.8163
1.7380
-
-
-
-
-
70.463775
70.650733
70.694409
70.709606
70.709613
BP86
4.
5.
6.
86.22
86.56
86.51
1.7054
1.7063
1.7055
1.6606
1.6592
1.6587
118.8
118.8
118.8
62.17
61.64
61.53
1.7326
1.7393
1.7387
1.6870
1.6879
1.6870
114.8
115.0
115.0
ecp-60-mwb[6s5p3d]:[2s1p]c
1.7133
1.6737
114.4
62.74
1.6728
114.7
62.28
1.6724
114.6
62.28
1.716
1.676
114.5
62.6
1.7037
1.6667
114.0
63.2
1.7165
1.7155
BLYP
1.
1.8205
1.7241
85.9
1.7006
1.6556
119.1
62.4
1.7203
1.6782
114.6
-
-
-
-
-
70.926389
71.154099
71.199158
71.214188
71.214481
2.
1.8193
1.7350
-
-
-
-
-
70.922087
71.126002
71.167400
71.181428
71.182290
1.8190
1.7419
-
-
-
-
-
70.295790
70.484842
70.519575
70.536962
70.536886
1.8143
1.7394
-
-
-
-
-
70.303640
70.489461
70.522852
70.541468
70.540802
1.8203
1.7425
-
-
-
-
-
70.313915
70.495274
70.527534
70.547866
70.546917
1.8186
1.7420
-
-
-
-
-
70.317252
70.497074
70.529095
70.549397
70.548425
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
BLYP/EC60[4s3p3d]:[2s1p]d
1.816
1.737
85.4
1.708
1.656
118.8
61.5
1.735
1.685
115.0
3.
4.
5.
6.
85.9
86.2
86.4
86.7
86.6
1.7109
1.7172
1.7156
1.7167
1.7168
1.6628
1.6696
1.6668
1.6662
1.6656
119.0
119.2
119.3
119.3
119.3
62.4
62.2
62.2
61.9
61.8
1.7351
1.7399
1.7382
1.7443
1.7430
1.6892
1.6956
1.6926
1.6927
1.6926
114.7
114.5
114.4
114.5
114.5
1.7165
1.6761
113.9
63.2
1.6833
113.6
63.4
1.6793
113.6
63.4
1.6796
113.8
63.2
1.6788
113.7
63.1
1.701
1.655
116.7
60.7
1.715
1.669
114.5
62.4
1.7223
1.7201
1.7241
1.7239
B3LYP
1.
4.
5.
6.
ACM/EC60[4s3p3d]:[2s1p]d
1.8063
1.7115
86.0
-
-
-
-
-
70.939280
71.158160
71.202934
71.216815
71.217686
1.8029
1.7279
-
-
-
-
-
70.301838
70.479115
70.511384
70.529519
70.529276
1.8084
1.7315
-
-
-
-
-
70.314208
70.486662
70.517165
70.537522
70.536893
1.8068
1.7311
-
-
-
-
-
70.317882
70.488587
70.518835
70.539170
70.538509
1.804
1.722
85.4
1.689
1.636
118.2
61.5
1.722
1.666
115.4
1.8158
1.7367
85.6
1.7251
1.6806
119.6
62.9
1.7538
1.7029
113.4
-
-
86.4
86.7
86.7
1.6912
1.7062
1.7088
1.7080
1.6426
1.6529
1.6529
1.6522
119.1
119.3
119.4
119.4
62.1
62.0
61.5
61.5
1.7117
1.7298
1.7379
1.7363
1.6659
1.6807
1.6828
1.6819
114.7
114.4
114.5
114.5
1.6936
1.6534
114.2
62.9
1.6667
113.6
63.3
1.6673
113.8
62.9
1.6667
113.8
62.9
1.699
1.649
115.5
61.6
1.7284
1.6928
111.7
64.4
1.7112
1.7155
1.7147
MP2
LANL2[3s4p2d]:[2s] (Frenking II)
-
-
-
1.
4.
5.
6.
EC60[4s3p3d]:[2s1p]d
70.440944
70.610466
70.638463
1.7740
1.6950
-
-
-
-
-
70.429502
70.621449
70.663095
70.671328
70.673801
1.7800
1.7075
-
-
-
-
-
69.891614
70.069595
70.115904
70.124687
70.125802
1.7909
1.7237
-
-
-
-
-
70.031655
70.196123
70.249846
70.258366
70.259972
1.7841
1.7163
-
-
-
-
-
70.057834
70.221691
70.279718
70.286512
70.288405
1.777
1.708
85.4
1.684
1.623
119.0
59.5
1.718
1.654
114.8
1.7862
1.7151
85.8
1.6941
1.6427
119.6
61.2
1.7166
1.6690
114.0
-
-
85.7
86.0
86.7
86.8
1.6760
1.6770
1.6871
1.6764
70.648927
1.6216
1.6334
1.6491
1.6371
119.4
119.0
117.7
117.3
61.0
60.6
60.8
60.7
1.7033
1.7104
1.7351
1.7296
70.651666
1.6443
1.6585
1.6760
1.6656
114.3
114.8
115.6
115.8
1.6786
1.6304
113.5
61.9
1.6447
114.4
61.7
1.6606
116.0
60.2
1.6493
116.3
60.1
1.691
1.635
114.5
60.3
1.6976
1.6564
112.8
63.5
1.6861
1.7046
1.6959
CCSD(T)
4.
-
-
-
5.
6.
69.933433
70.106621
70.139642
1.7982
1.7330
-
-
-
-
-
70.082412
70.239669
70.275187
70.291849
70.291899
1.7906
1.7247
-
-
-
-
-
70.107037
70.263530
70.302946
70.318079
70.318329
-
-
-
-
-
70.531207
70.716142
70.756708
70.765064
70.766733
-
-
-
-
-
69.890717
70.068861
70.114641
70.123836
70.124688
-
-
-
-
-
69.932997
70.106286
70.139215
70.153427
70.153698
-
-
-
-
-
69.933371
70.106516
70.138759
70.153401
70.153401
-15290.
-15290.
-15290.
-15290.
-15290.
86.5
86.6
1.7080
1.6966
70.153725
1.6566
1.6428
119.1
118.87
61.0
60.92
1.7429
1.7365
70.154080
1.6863
1.6750
114.6
114.8
1.7176
1.7083
Single point calculations
MP2/III//MP2/IIe
MP2//B3LYP Basis set 4.
CCSD(T)//B3LYP Basis set 4.
CCSD(T)//MP2 Basis set 4.
RHF/Basis set 7f
1.6704
114.3
62.0
1.6577
114.62
61.72
RHF+R/Basis set 7f
D-K RHF/Basis set 7f
MCPF/Basis set 7f
MCPF+R/Basis set 7f
D-K MCPF/Basis set 7f
a
680257
854022
902708
913402
-16035.
-16035.
-16035.
-16035.
393745
511965
511634
540165
-16043.
-16043.
-16043.
-16043.
-16043.
684750
807399
805954
835489
834828
-15291.
-15291.
-15291.
-15291.
-15291.
203882
380563
458112
458968
461501
-16035.
-16036.
-16036.
-16036.
-16036.
905990
026830
058619
075362
075084
-16044.
-16044.
-16044.
-16044.
-16044.
027567
182433
220637
235570
237586
The definition of the geometrical parameters is as follows:
915439
Use Wo rd
6.0 c
or la te r to
vi ew Ma ci nto sh pi c tu
re.
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].
f
All-electron basis set 7 = [18s17p12d5f]:[3s2p]. Geometries were optimized at CCSD(T)/Basis set 6.
Supporting Information Table III. Vibrational frequencies (cm -1) and infrared intensities (km/mole) for
WH6 isomers calculated at MP2/Basis set 4
D3h
Oh
Freq
Intensity
Freq
C3v B
Intensity
C5v
C3v A
(stag-
(eclipsed
gered)
)
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
2040
0
2096
0
2200
32
2131
194
2165
64
for
Economical Treatments of Relativistic Effects
and Electron Correlation in WH6
Roland H. Hertwig, Wolfram Koch and Brian F. Yates
Supporting Information Table I.
Complete list of relative energies (kJ/mol) for WH 6 isomers
Oh
D3h
C3v B
C5v
(staggered)
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
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
1056
277.5
7.5
11.3
0.0
BP iop(5/42=46) (G94)
LANL1[2s2p2d]:[2s]
105
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
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
IVa + relativistic core potential
840.2
205.7
25.4
2.5
0.0
ADF calcs, Becke-Perdew
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
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
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
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
553.3
108.2
34.7
7.2
0.0
BP86
BLYP
B3LYP
MP2
LANL2[3s4p2d]:[2s] (Frenking II)
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
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
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
RHF/Basis set 7f
617.5
161.3
33.4
5.3
0.0
CCSD(T)
Single point calculations
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].
f All-electron basis set 7 = [18s17p12d5f]:[3s2p]. Geometries were optimized at CCSD(T)/Basis set 6.
Supporting Information Table II. Geometries a ( and degree) and total energies (Hartree) for WH 6 isomers
Oh
D3h
C3v B
C5v
C3v A
(staggered)
(eclipsed)
r2
1
2
r
r
r1
r1
r2
r1
1.7812
1.6983
86.4
1.7021
-
-
-
-
-
70.210417
70.377038
70.400201
70.416573
70.418671
1.7917
1.7176
-
-
-
-
-
70.204311
70.349230
70.368331
70.384390
70.387409
1.7899
1.7215
-
-
-
-
-
69.518727
69.653691
69.665375
69.685221
89.687008
1.7829
1.7168
-
-
-
-
-
69.538881
69.670063
69.677578
69.700431
69.701629
r2
1
2
RHF
1. LANL2[3s3p2d]:[2s1p]
2. SKBJ[4s4p3d]:[2s1p]
3. ecp-60-mwb[6s5p3d]:[2s1p]
4. ecp-60-mwb[6s5p3d1f]:[2s1p]
86.6
86.5
86.6
1.7197
1.7229
1.7191
1.6272
1.6400
1.6448
1.6396
119.8
119.8
119.9
120.0
61.6
61.9
61.7
61.6
1.7130
1.7382
1.7365
1.7321
1.6558
1.6743
1.6783
1.6738
113.7
113.7
113.4
113.4
1.6955
1.7171
1.7188
1.7147
1.6407
112.8
63.5
1.6574
112.6
63.8
1.6625
111.9
64.2
1.6574
111.5
64.4
5. ecp-60-mwb[6s5p4d2f]:[3s2p]
1.7912
1.7247
-
-
-
-
-
69.562439
69.688563
69.691146
69.718134
69.718526
1.7886
1.7235
-
-
-
-
-
69.567639
69.691389
69.693593
69.720565
69.720915
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
Basis set G. [19s17p11d4f]:[5s2p] b
1.833
1.741
86.6
1.720
1.639
118.3
60.5
1.760
1.679
EC60[4s3p3d]:[2s1p]d
1.784
1.714
86.1
1.716
1.632
119.9
60.9
1.732
BP iop(5/42=46) (G94)
1.9853
1.7754
85.2
1.6889
1.6398
115.2
63.8
1.7417
LANL1[2s2p2d]:[2s]
-
-
-
-
-
11.160838
11.457474
11.560306
11.558871
11.563175
1.9891
1.7788
-
-
-
-
-
10.951877
11.245711
11.346542
11.345579
11.349759
1.9854
1.7779
-
-
6. ecp-60-mwb[6s5p4d3f]:[5s2p1d]
BP86 (G94)
BP (Turbo)
LANL1[2s2p2d]:[2s]
LANL1[2s2p2d]:[2s]
86.9
86.8
85.2
85.1
1.7264
1.7261
1.6932
1.6928
-
1.6429
1.6416
1.6431
1.6427
120.0
120.0
115.3
115.4
60.9
60.86
63.8
63.7
1.7434
1.7432
1.7458
1.7450
-
1.6785
1.6609
111.4
64.3
1.6598
111.3
64.27
1.720
1.651
116.0
61.3
115.9
1.728
1.656
116.1
61.2
1.666
113.9
1.712
1.647
112.7
63.3
1.6794
116.9
1.7119
1.6575
117.9
61.4
1.6610
117.8
61.4
1.6603
117.8
61.4
1.6774
1.6829
1.6820
113.3
113.3
116.9
116.9
1.7224
1.7218
1.7162
1.7152
-
10.948101
11.243394
1.9437
1.8055
-0.589368
-0.863923
1.9127
1.7895
-0.598797
-0.880734
1.8596
1.7572
-0.676114
-0.924514
1.9422
1.8251
-0.659144
-0.893704
1.9087
1.8070
-0.676253
-0.917921
1.8984
1.7787
-0.657979
-0.896826
1.8614
1.7598
-0.666675
-0.904287
1.7801
1.7127
11.345012
11.343723
11.348216
ADF calcs, Becke-Perdew
II [2s1p2d]:[2s]
IV [3s1p3d]:[3s1p]
IV [5s3p3d3f]:[3s1p]
II + relativistic core potential
IV [3s1p3d] + relativistic core potential
II + relativistic core potential +
scalar/pauli
IV [3s1p3d] + relativistic core potential + scalar/pauli
IV [5s3p3d3f] + relativistic core po-
85.3
1.7550
1.7155
117.1
63.2
-0.952871
85.0
1.7355
1.7066
1.6946
116.5
62.2
1.7864
1.6677
116.1
61.86
1.7635
1.7369
117.6
62.7
1.7408
1.7168
117.8
61.5
1.7208
1.7020
118.6
62.9
1.6875
1.7484
1.8156
1.7966
1.7654
1.6757
118.5
61.9
1.7473
1.6957
116.6
119.0
61.44
1.7077
116.7
62.2
1.7495
1.7063
117.2
61.0
1.7254
1.6787
117.4
60.98
1.7539
115.8
62.5
1.7315
116.1
61.3
1.7132
114.5
63.4
1.6894
115.3
62.0
1.6584
113.7
62.54
-1.011688
1.7690
115.8
1.7956
-0.968065
1.7478
116.1
1.7745
-0.996253
1.7232
115.1
1.7483
-0.969251
1.7013
115.5
-0.979879
1.6435
1.7291
-0.975726
-0.968934
-0.968436
85.62
116.8
-0.995309
-0.958410
87.2
1.7237
-0.965824
-0.986593
87.8
1.7716
1.7669
-0.952707
-1.008605
-0.963228
86.4
116.4
-0.972869
-1.008952
86.4
1.7423
-0.949169
-0.972539
84.14
1.7862
1.7286
-0.980183
1.6694
114.4
1.6929
tential + scalar/pauli
-1.159547
-1.340667
-1.372997
-1.392705
-1.391547
1.8139
1.7354
-
-
-
-
-
70.449640
70.642362
70.687253
70.700462
70.700782
1.8186
1.7388
-
-
-
-
-
70.460403
70.648930
70.692836
70.708023
70.708051
1.8163
1.7380
-
-
-
-
-
70.463775
70.650733
70.694409
70.709606
70.709613
BP86
4.
5.
6.
86.22
86.56
86.51
1.7054
1.7063
1.7055
1.6606
1.6592
1.6587
118.8
118.8
118.8
62.17
61.64
61.53
1.7326
1.7393
1.7387
1.6870
1.6879
1.6870
114.8
115.0
115.0
ecp-60-mwb[6s5p3d]:[2s1p]c
1.7133
1.6737
114.4
62.74
1.6728
114.7
62.28
1.6724
114.6
62.28
1.716
1.676
114.5
62.6
1.7037
1.6667
114.0
63.2
1.7165
1.7155
BLYP
1.
1.8205
1.7241
85.9
1.7006
1.6556
119.1
62.4
1.7203
1.6782
114.6
-
-
-
-
-
70.926389
71.154099
71.199158
71.214188
71.214481
2.
1.8193
1.7350
-
-
-
-
-
70.922087
71.126002
71.167400
71.181428
71.182290
1.8190
1.7419
-
-
-
-
-
70.295790
70.484842
70.519575
70.536962
70.536886
1.8143
1.7394
-
-
-
-
-
70.303640
70.489461
70.522852
70.541468
70.540802
1.8203
1.7425
-
-
-
-
-
70.313915
70.495274
70.527534
70.547866
70.546917
1.8186
1.7420
-
-
-
-
-
70.317252
70.497074
70.529095
70.549397
70.548425
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
BLYP/EC60[4s3p3d]:[2s1p]d
1.816
1.737
85.4
1.708
1.656
118.8
61.5
1.735
1.685
115.0
3.
4.
5.
6.
85.9
86.2
86.4
86.7
86.6
1.7109
1.7172
1.7156
1.7167
1.7168
1.6628
1.6696
1.6668
1.6662
1.6656
119.0
119.2
119.3
119.3
119.3
62.4
62.2
62.2
61.9
61.8
1.7351
1.7399
1.7382
1.7443
1.7430
1.6892
1.6956
1.6926
1.6927
1.6926
114.7
114.5
114.4
114.5
114.5
1.7165
1.6761
113.9
63.2
1.6833
113.6
63.4
1.6793
113.6
63.4
1.6796
113.8
63.2
1.6788
113.7
63.1
1.701
1.655
116.7
60.7
1.715
1.669
114.5
62.4
1.7223
1.7201
1.7241
1.7239
B3LYP
1.
4.
5.
6.
ACM/EC60[4s3p3d]:[2s1p]d
1.8063
1.7115
86.0
-
-
-
-
-
70.939280
71.158160
71.202934
71.216815
71.217686
1.8029
1.7279
-
-
-
-
-
70.301838
70.479115
70.511384
70.529519
70.529276
1.8084
1.7315
-
-
-
-
-
70.314208
70.486662
70.517165
70.537522
70.536893
1.8068
1.7311
-
-
-
-
-
70.317882
70.488587
70.518835
70.539170
70.538509
1.804
1.722
85.4
1.689
1.636
118.2
61.5
1.722
1.666
115.4
1.8158
1.7367
85.6
1.7251
1.6806
119.6
62.9
1.7538
1.7029
113.4
-
-
86.4
86.7
86.7
1.6912
1.7062
1.7088
1.7080
1.6426
1.6529
1.6529
1.6522
119.1
119.3
119.4
119.4
62.1
62.0
61.5
61.5
1.7117
1.7298
1.7379
1.7363
1.6659
1.6807
1.6828
1.6819
114.7
114.4
114.5
114.5
1.6936
1.6534
114.2
62.9
1.6667
113.6
63.3
1.6673
113.8
62.9
1.6667
113.8
62.9
1.699
1.649
115.5
61.6
1.7284
1.6928
111.7
64.4
1.7112
1.7155
1.7147
MP2
LANL2[3s4p2d]:[2s] (Frenking II)
-
-
-
1.
4.
5.
6.
EC60[4s3p3d]:[2s1p]d
70.440944
70.610466
70.638463
1.7740
1.6950
-
-
-
-
-
70.429502
70.621449
70.663095
70.671328
70.673801
1.7800
1.7075
-
-
-
-
-
69.891614
70.069595
70.115904
70.124687
70.125802
1.7909
1.7237
-
-
-
-
-
70.031655
70.196123
70.249846
70.258366
70.259972
1.7841
1.7163
-
-
-
-
-
70.057834
70.221691
70.279718
70.286512
70.288405
1.777
1.708
85.4
1.684
1.623
119.0
59.5
1.718
1.654
114.8
1.7862
1.7151
85.8
1.6941
1.6427
119.6
61.2
1.7166
1.6690
114.0
-
-
85.7
86.0
86.7
86.8
1.6760
1.6770
1.6871
1.6764
70.648927
1.6216
1.6334
1.6491
1.6371
119.4
119.0
117.7
117.3
61.0
60.6
60.8
60.7
1.7033
1.7104
1.7351
1.7296
70.651666
1.6443
1.6585
1.6760
1.6656
114.3
114.8
115.6
115.8
1.6786
1.6304
113.5
61.9
1.6447
114.4
61.7
1.6606
116.0
60.2
1.6493
116.3
60.1
1.691
1.635
114.5
60.3
1.6976
1.6564
112.8
63.5
1.6861
1.7046
1.6959
CCSD(T)
4.
-
-
-
5.
6.
69.933433
70.106621
70.139642
1.7982
1.7330
-
-
-
-
-
70.082412
70.239669
70.275187
70.291849
70.291899
1.7906
1.7247
-
-
-
-
-
70.107037
70.263530
70.302946
70.318079
70.318329
-
-
-
-
-
70.531207
70.716142
70.756708
70.765064
70.766733
-
-
-
-
-
69.890717
70.068861
70.114641
70.123836
70.124688
-
-
-
-
-
69.932997
70.106286
70.139215
70.153427
70.153698
-
-
-
-
-
69.933371
70.106516
70.138759
70.153401
70.153401
-15290.
-15290.
-15290.
-15290.
-15290.
86.5
86.6
1.7080
1.6966
70.153725
1.6566
1.6428
119.1
118.87
61.0
60.92
1.7429
1.7365
70.154080
1.6863
1.6750
114.6
114.8
1.7176
1.7083
Single point calculations
MP2/III//MP2/IIe
MP2//B3LYP Basis set 4.
CCSD(T)//B3LYP Basis set 4.
CCSD(T)//MP2 Basis set 4.
RHF/Basis set 7f
1.6704
114.3
62.0
1.6577
114.62
61.72
RHF+R/Basis set 7f
D-K RHF/Basis set 7f
MCPF/Basis set 7f
MCPF+R/Basis set 7f
D-K MCPF/Basis set 7f
a
680257
854022
902708
913402
-16035.
-16035.
-16035.
-16035.
393745
511965
511634
540165
-16043.
-16043.
-16043.
-16043.
-16043.
684750
807399
805954
835489
834828
-15291.
-15291.
-15291.
-15291.
-15291.
203882
380563
458112
458968
461501
-16035.
-16036.
-16036.
-16036.
-16036.
905990
026830
058619
075362
075084
-16044.
-16044.
-16044.
-16044.
-16044.
027567
182433
220637
235570
237586
The definition of the geometrical parameters is as follows:
915439
Use Wo rd
6.0 c
or la te r to
vi ew Ma ci nto sh pi c tu
re.
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].
f
All-electron basis set 7 = [18s17p12d5f]:[3s2p]. Geometries were optimized at CCSD(T)/Basis set 6.
Supporting Information Table III. Vibrational frequencies (cm -1) and infrared intensities (km/mole) for
WH6 isomers calculated at MP2/Basis set 4
D3h
Oh
Freq
Intensity
Freq
C3v B
Intensity
C5v
C3v A
(stag-
(eclipsed
gered)
)
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
2040
0
2096
0
2200
32
2131
194
2165
64