suppmat1604. 45KB Jun 05 2011 09:30:47 PM

Supporting Information

for

Economical Treatments of Relativistic Effects

and Electron Correlation in WH

₆

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

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].}

5

Supporting Information Table II. Geometriesa _{(Å and degree) and total energies (Hartree) for WH}

6 isomers

Oh D3h C3v B

(staggered)

C5v C3v A

(eclipsed)

r r θ r1 r2 θ1 θ2 r1 r2 θ r1 r2 θ1 θ2

RHF

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

-69.562439

1.7247

-69.688563

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)

LANL1[2s2p2d]:[2s]

1.9853

-11.160838

1.7754

-11.457474

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

7

BP (Turbo) LANL1[2s2p2d]:[2s] 1.9854

-10.948101

1.7779

-11.243394

85.1 1.6928

-11.345012

1.6427 115.4 63.7 1.7450

-11.343723

1.6820 116.9 1.7152

-11.348216

1.6603 117.8 61.4

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 +

sca-lar/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

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

IV [5s3p3d3f] + relativistic core

po-tential + scalar/pauli

1.7801

-1.159547

1.7127

-1.340667

85.62 1.6875

-1.372997

1.6435 119.0 61.44 1.7077

-1.392705

1.6694 114.4 1.6929

-1.391547

1.6584 113.7 62.54

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

9

85.9 1.7006

-71.199158

1.6556 119.1 62.4 1.7203

-71.214188

1.6782 114.6 1.7037

-71.214481

1.6667 114.0 63.2

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

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}

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 1.715 1.669 114.5 62.4}

B3LYP

1. 1.8063

-70.939280

1.7115

-71.158160

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

-70.301838

1.7279

-70.479115

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

-70.314208

1.7315

-70.486662

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

-70.317882

1.7311

-70.488587

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

11

MP2

LANL2[3s4p2d]:[2s] (Frenking II) 1.8158

-70.440944

1.7367

-70.610466

85.6 1.7251

-70.638463

1.6806 119.6 62.9 1.7538

-70.648927

1.7029 113.4 1.7284

-70.651666

1.6928 111.7 64.4

1. 1.7740

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

CCSD(T)

4. 1.7862

-69.933433

1.7151

-70.106621

85.8 1.6941

-70.139642

1.6427 119.6 61.2 1.7166

-70.153725

1.6690 114.0 1.6976

-70.154080

1.6564 112.8 63.5

5. 1.7982

-70.082412

1.7330

-70.239669

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

-70.107037

1.7247

-70.263530

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

-70.531207

-70.716142

-70.756708

-70.765064

-70.766733

MP2//B3LYP Basis set 4.

-69.890717

-70.068861

-70.114641

-70.123836

-70.124688

-13

CCSD(T)//MP2 Basis set 4.

-69.933371

-70.106516

-70.138759

-70.153401

-70.153401

RHF/Basis set 7f _-15290.

680257

-15290.

854022

-15290.

902708

-15290.

913402

-15290.

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

W

H H

H

H _H H

W

H H

H

H H

H

W

H H

H

H H

H W

H

H H

H H H

C

_3v

staggered

D

_3h

_C

3v

eclipsed

C

_5v

r

r

₂

r

₁

r

₁

r

₂

r

₁

r

₂

θ

θ

θ

1

θ

₂

θ

₁

θ

₂

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