supp_1702_figs. 280KB Jun 05 2011 09:30:50 PM

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Legends for Figures S1-S8:

FIGURE S1. The seven distinct rotational isomers of DP (of a 30o_torsional

search) viewed along P-P projection axis.

FIGURE S2. The six conformational groups, each being represented by its extended (180o_{, 180}o_{) conformation, of TP, as viewed through two adjacent P-P}

axes, separately.

FIGURE S3. The (t1, t1’) conformational energy surface of DP (HF/ 6-31G*

results).

FIGURE S4. Structures of the four energy minima of MDP identified on the HF/ 6-31G* surface, with the shortest C-H...O distance indicated. Partial charges derived from Mulliken population analysis for each atom are labeled.

FIGURE S5. Structure of the stg-stg extended conformation of TP, the energy

minimum identified on the HF/ 6-31G* surface.

FIGURE S6. The lowest vibrational mode and frequency associated with P-O-P bending for DP, MDP (gg I), and TP (symmetric and asymmetric), respectively.

Parenthesized numbers denote the order of the particular mode in the 3N-6 vibrational modes of the molecule (3 being the third lowest, for example).

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O O O O O P O O O O P O O O P O O P O O O P O O O P O O O O O O P O O O O

O O O O

O O

O

O O

O

P P _P P

stg

skw

I

II

eclp

I

II

III

short contact

I

II

O _O

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(4)

(5)

P

P P P

P P P P

(6)

P

180

146.0

1.6309A

1.7076A

(7)

81 cm

−1

DP (3)

145 cm

−1

TP (6)

106 cm

−1

MDP ggI (3)

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(9)

14

36

81

283

320

321

418

435

564

566

593

603

614

728

902

1007

1040

1157

1158

1179

1181

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34

65

106

140

195

235

274

314

329

418

436

517

563

581

591

619

662

765

987

1071

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1187

1223

1242

1261

1306

1323

1349

1630

1675

1688

3047

3110

3261

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40

53

99

114

166

241

273

307

329

423

438

520

557

579

588

618

654

776

986

1070

(13)

1184

1226

1240

1264

1304

1314

1340

1629

1650

1680

3024

3235

3307

(14)

29

54

106

153

189

233

277

312

334

414

434

528

561

587

588

607

655

783

988

1071

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1181

1224

1241

1265

1311

1314

1345

1624

1667

1692

3063

3127

3272

(16)

25

32

55

101

140

223

263

305

320

413

428

535

543

574

599

604

663

731

1008

1074

1207

1256

1265

1269

(17)

1291

1306

1323

1611

1639

1670

3059

3121

3193

(18)

20

38

62

75

89

145

180

300

302

315

346

426

442

460

524

557

574

580

594

609

628

713

718

859

(19)

968

1021

1039

1142

1180

1183

1198

1205

1283

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FIGURE S8. Normal mode vectors and frequencies (in cm-1_{) listed in increasing}

order for the minimum-energy structures of DP, MDP, and TP optimized with HF/ 6-31G*. These were created with the Gaussian94 output files and using the