Propellants Explos. Pyrotech. 2015 · © WILEY-VCH Verlag GmbH & Co. KGaA, 69451 Weinheim, 2015 · ISSN
0721–3115
SUPPORTING INFORMATION
Title: On the Comparison of Small Nitrogen and Phosphorus Oxide Cages
Author(s): R. J. Buszek, J. A. Boatz*
Ref. No.: prep.201500227
On the Comparison of Small Nitrogen and
Phosphorus Oxide Cages
Supplementary Information
Robert J. Buszek1 and Jerry A. Boatz2
1
2
ERC, Inc. Edwards Air Force Base, California 93524
Propellants Branch, Air Force Research Laboratory, Edwards Air Force Base, California 93524
[email protected]
Supplementary Table 1. Total energies of all stationary points (in hartrees, including unscaled zero point energies (ZPE.) )
B3PW91
MP2
aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ
aug-cc-pVDZ aug-cc-pVTZ aug-cc-pVQZ
aug-cc-pVDZ
-908.285274
-908.383450
-908.407352
-906.953154
-907.231084
-907.321630
-907.000853
c-P2O3
‡
aug-cc-pVTZ
-907.283316
CCSD(T)
aug-cc-pVQZ
-907.368732
aug-cc-pV5Z
-907.396501
CBS (Q-5)
-907.418306
[P2O3]
-908.271119
-908.369111
-908.392999
-906.941436
-907.218053
-907.307900
-906.987655
-907.269161
-907.353719
-907.381451
-907.402998
P2O3
-908.309197
-908.409903
-908.433758
-906.987794
-907.262445
-907.350963
-907.031245
-907.312855
-907.396052
-907.435205
-907.456093
-621.481177
-621.568136
-621.591548
-620.486534
-620.761078
-620.850532
-620.536662
-620.813631
-620.897012
-620.924458
-620.946137
[PO3N]
-621.476610
-621.563049
-621.586536
-620.483055
-620.755621
-620.844927
-620.530172
-620.807634
-620.890883
-620.918187
-620.939969
PO3N
-621.594902
-621.683157
-621.706959
-620.614124
-620.883006
-620.972236
-620.652326
-620.926639
-621.009956
-621.037202
-621.058585
c-PO3N
‡
c-N2O6
‡
-559.025092
[N2O6]
-559.024363
c-N4O6
-668.229361
‡
[N4O6]
-668.227233
Supplementary Table 2. Cartesian Coordinates (Å) at the CCSD(T)/aug-cc-pVQZ level of theory
X
Y
Z
c-P2O3
P
-2.55520949
1.670881654
-0.169665493
O
-1.719091214
2.251014584
1.185150502
O
-1.604699795
0.284496049
0.045227752
O
-1.218430825
2.250180304
-1.035407468
P
-0.472850777
1.51982172
0.299465837
[P2O3]‡
P
O
O
O
P
-2.58018155
-1.417455504
-1.739545928
-1.341631413
-0.473830091
1.555364714
2.296666717
0.295015787
2.294212763
1.579249547
-0.391207822
1.380280684
0.059612711
-1.038178473
0.41565993
P2O3
P
O
O
O
P
-2.734554123
-0.798220454
-2.786425008
-1.261385882
-0.138431903
1.277009243
2.282016483
0.03411261
1.98358349
2.150615842
-0.839017379
1.816183063
-0.063839944
-0.672620388
0.513934155
c-PO3N
N
O
O
O
P
-2.373497297
-1.765799005
-1.656756256
-1.287618586
-0.486610956
1.657727631
2.226252654
0.346404588
2.225355059
1.520654378
-0.128674273
1.123018862
0.033367165
-0.999370841
0.296430218
[PO3N]‡
N
O
O
O
P
-2.444163514
-1.826081218
-1.721831853
-1.096274804
-0.465206875
1.543684099
2.173081771
0.358673189
2.29177691
1.563424656
0.032147402
1.102839946
0.002453229
-1.074110569
0.184951514
PO3N
N
O
O
O
P
-2.567241777
-3.365894507
-1.452029529
-0.238257443
-0.197936744
2.127908474
1.843585191
0.933745199
2.336013412
1.085367725
0.614014269
1.366963198
0.57812672
-1.195873615
-0.420250573
Supplementary Table 3. Frequencies (cm-1) at the CCSD(T)/aug-cc-pVQZ level of theory
Frequencies (cm-1)
c-P2O3
382
382
538
538
742
767
787
898
786
[P2O3]‡
170
1085
439
309i
463
571
630
928
974
P2O3
70
1270
72
1285
101
384
491
594
864
c-PO3N
413
923
413
971
646
647
660
777
777
[PO3N]‡
211
1028
526
436i
570
599
805
847
951
PO3N
42
1259
148
1871
158
362
446
642
893
Supplementary Table 4. CBS total energies (in hartrees,) excluding ZPE corrections.
Optimized parameters
SCF=
1.1099137
CCSD=
1.9303174
(T)=
1.8104726
a
CCSD(T)/aug-cc-pVQZ
CCSD(T)/aug-cc-pV5Z
SCF
CCSD
(T)
Etot
SCF
c-P2O3
-906.265054
-1.062179
-0.054740
-907.381973
-906.269748
-1.083619
[P2O3]‡
-906.240675
-1.067091
-0.057925
-907.365691
-906.245629
-1.088242
P2O3
-906.295140
-1.056988
-0.055587
-907.407715
-906.300634
-619.713069
-1.134881
-0.063224
-620.911174
-619.693355
-1.140361
-0.069748
-620.903464
c-PO3N
‡
[PO3N]
-619.839452
-1.120753
-0.063008
-621.023214
PO3N
a
Parameters taken from D. W. Schwenke, J. Chem. Phys. 2005, 122 (1), 7.
CCSD
(T)
CCSD(T)/CBS(Q-5)
Etot
SCF
CCSD
(T)
Etot
-0.056396
-907.409763
-906.270264
-1.103565
-0.057738
-907.431568
-0.059561
-907.393433
-906.246173
-1.107920
-0.060887
-907.414980
-1.077484
-0.057087
-907.435205
-906.301238
-1.096553
-0.058302
-907.456093
-619.717545
-1.156177
-0.064921
-620.938644
-619.718037
-1.175990
-0.066296
-620.960323
-619.697548
-1.161746
-0.071507
-620.930801
-619.698009
-1.181641
-0.072934
-620.952583
-619.844044
-1.141753
-0.064663
-621.050460
-619.844549
-1.161289
-0.066005
-621.071843
Supplementary Figure 1. MP2/aug-cc-pVDZ intrinsic reaction coordinate(IRC) of the unimolecular decomposition of P2O3.
Supplementary Figure 2. MP2/aug-cc-pVDZ intrinsic reaction coordinate(IRC) of the unimolecular decomposition of PO3N.
Supplementary Figure 3. MP2/aug-cc-pVDZ intrinsic reaction coordinate(IRC) of the unimolecular decomposition of N2O6.
Supplementary Figure 4. MP2/aug-cc-pVDZ intrinsic reaction coordinate(IRC) of the unimolecular decomposition of N4O6