supp_1702_figs. 280KB Jun 05 2011 09:30:50 PM
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 , 180o ) 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).
FIGURE S7. Atom labeling of the three model molecules to which the geometric
parameters in Table S1 refer. Partial charges as determined by Mulliken
population are those for the lowest-energy structure of each compound.
stg
I
II
O
O
O
O
O
O
P
P
O
O
O
O
O
skw
O
II
I
O
O
O
O
O
O
O
O
O
eclp
O
P
O
P
O
I
II
III
O
O
O
P
P
P
O
O
O
O
O
O
O
O
O
O
short contact
O
P
P
P
P
O
O
O
O
O
stg−stg
O*
O*
X
X
stg−skw
O*
O*
X
X
skw−skw
O*
O*
X
X
stg−eclp
O*
O*
X
X
skw−eclp
O*
O*
X
X
eclp−eclp
O*
O*
X
X
X= O*PO3
−0.925
−0.925
−0.883
−0.928
−0.886
−0.875
−0.884
1.535
1.549
P
1.467
1.505
P
84
−0.903
O
−0.753
0.273
2.1
−54
2.4
−0.946
C −0.151
−0.898
0A
−0.756
H
H
5A
P
50
−0.953 O
−68
−0.943
P
C −0.150
0.217
0.144
0.014 0.058
−0.002
gg II
gg I
−0.926
−0.875
−0.925
−0.932
−0.879
P
−0.931
1.460
1.538
1.475
−0.844
P
P
−27
−0.901
87
−168
−0.911
−57
1.545
P
−0.898
O
2.60A
O
−0.945
−0.745
0.256
2.1
9A
H
C
−0.929
−0.722
−0.070
−0.150
0.068
H
0.031
0.020
cg
0.079
C
gt
0.112
P
180
.0
A
146
P
9
30
1.6
1.7076A
180
P
81 cm−1
DP (3)
75 cm−1
TP (4)
106 cm−1
MDP ggI (3)
−1
145 cm
TP (6)
Diphosphate
−0.994
O1
O8
−1.000
−1.005
1.449
O9
1.449
P2
P4
O3
−0.900
O7
−0.994
O6
−1.005
O5
−1.000
Methyl diphosphate
−0.925
−0.883
O1
O13
−0.928
−0.875
O10
O3
1.549
P4
P2
1.467
O11
−0.903
O5
O12
−0.753
−0.943
H7
0.273
C6 −0.151
H8
H9 0.058
Triphosphate
−0.926
0.014
−0.926 O9
O8
−0.980
−0.980
O11
O1
P4
1.592
1.463
P2
O6
O7 −0.983
−0.983
1.463
O3
−0.887
O5
P10
−0.887
O12
O13 −0.983
−0.983
14
36
81
283
320
321
418
435
564
566
593
603
614
728
902
1007
1040
1157
1158
1179
DP
1181
34
65
106
140
195
235
274
314
329
418
436
517
563
581
591
619
662
765
987
1071
MDP ggI
1187
1223
1242
1261
1306
1323
1349
1630
1675
1688
3047
3110
3261
MDP ggI
40
53
99
114
166
241
273
307
329
423
438
520
557
579
588
618
654
776
986
1070
MDPggII
1184
1226
1240
1264
1304
1314
1340
1629
1650
1680
3024
3307
MDPggII
3235
29
54
106
153
189
233
277
312
334
414
434
528
561
587
588
607
655
783
988
1071
MDP cg
1181
1224
1241
1265
1311
1314
1345
1624
1667
1692
3063
3127
3272
MDP cg
25
32
55
101
140
223
263
305
320
413
428
535
543
574
599
604
731
1008
663
1207
1256
1265
MDPgt
1074
1269
1291
1306
1323
1611
1639
1670
3059
3121
3193
MDPgt
20
38
62
75
89
145
180
300
302
315
346
426
442
460
524
557
574
580
594
609
628
713
718
859
TP
968
1021
1039
1142
1180
1183
1198
1205
1283
TP
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
vibs.c’ program retrieved from an archived file of the Computational
Chemistry List (http:/ / ccl.osc.edu/ chemistry/ html).
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 , 180o ) 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).
FIGURE S7. Atom labeling of the three model molecules to which the geometric
parameters in Table S1 refer. Partial charges as determined by Mulliken
population are those for the lowest-energy structure of each compound.
stg
I
II
O
O
O
O
O
O
P
P
O
O
O
O
O
skw
O
II
I
O
O
O
O
O
O
O
O
O
eclp
O
P
O
P
O
I
II
III
O
O
O
P
P
P
O
O
O
O
O
O
O
O
O
O
short contact
O
P
P
P
P
O
O
O
O
O
stg−stg
O*
O*
X
X
stg−skw
O*
O*
X
X
skw−skw
O*
O*
X
X
stg−eclp
O*
O*
X
X
skw−eclp
O*
O*
X
X
eclp−eclp
O*
O*
X
X
X= O*PO3
−0.925
−0.925
−0.883
−0.928
−0.886
−0.875
−0.884
1.535
1.549
P
1.467
1.505
P
84
−0.903
O
−0.753
0.273
2.1
−54
2.4
−0.946
C −0.151
−0.898
0A
−0.756
H
H
5A
P
50
−0.953 O
−68
−0.943
P
C −0.150
0.217
0.144
0.014 0.058
−0.002
gg II
gg I
−0.926
−0.875
−0.925
−0.932
−0.879
P
−0.931
1.460
1.538
1.475
−0.844
P
P
−27
−0.901
87
−168
−0.911
−57
1.545
P
−0.898
O
2.60A
O
−0.945
−0.745
0.256
2.1
9A
H
C
−0.929
−0.722
−0.070
−0.150
0.068
H
0.031
0.020
cg
0.079
C
gt
0.112
P
180
.0
A
146
P
9
30
1.6
1.7076A
180
P
81 cm−1
DP (3)
75 cm−1
TP (4)
106 cm−1
MDP ggI (3)
−1
145 cm
TP (6)
Diphosphate
−0.994
O1
O8
−1.000
−1.005
1.449
O9
1.449
P2
P4
O3
−0.900
O7
−0.994
O6
−1.005
O5
−1.000
Methyl diphosphate
−0.925
−0.883
O1
O13
−0.928
−0.875
O10
O3
1.549
P4
P2
1.467
O11
−0.903
O5
O12
−0.753
−0.943
H7
0.273
C6 −0.151
H8
H9 0.058
Triphosphate
−0.926
0.014
−0.926 O9
O8
−0.980
−0.980
O11
O1
P4
1.592
1.463
P2
O6
O7 −0.983
−0.983
1.463
O3
−0.887
O5
P10
−0.887
O12
O13 −0.983
−0.983
14
36
81
283
320
321
418
435
564
566
593
603
614
728
902
1007
1040
1157
1158
1179
DP
1181
34
65
106
140
195
235
274
314
329
418
436
517
563
581
591
619
662
765
987
1071
MDP ggI
1187
1223
1242
1261
1306
1323
1349
1630
1675
1688
3047
3110
3261
MDP ggI
40
53
99
114
166
241
273
307
329
423
438
520
557
579
588
618
654
776
986
1070
MDPggII
1184
1226
1240
1264
1304
1314
1340
1629
1650
1680
3024
3307
MDPggII
3235
29
54
106
153
189
233
277
312
334
414
434
528
561
587
588
607
655
783
988
1071
MDP cg
1181
1224
1241
1265
1311
1314
1345
1624
1667
1692
3063
3127
3272
MDP cg
25
32
55
101
140
223
263
305
320
413
428
535
543
574
599
604
731
1008
663
1207
1256
1265
MDPgt
1074
1269
1291
1306
1323
1611
1639
1670
3059
3121
3193
MDPgt
20
38
62
75
89
145
180
300
302
315
346
426
442
460
524
557
574
580
594
609
628
713
718
859
TP
968
1021
1039
1142
1180
1183
1198
1205
1283
TP
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
vibs.c’ program retrieved from an archived file of the Computational
Chemistry List (http:/ / ccl.osc.edu/ chemistry/ html).