Products of the Reaction of P and O2
J. Phys. Chem. A, Vol. 104, No. 16, 2000 3571
TABLE 11: B3LYP/6-31+G* Harmonic Frequencies (cm-1),
Intensities (km/mol), and 16O to l8O Isotopic Ratios for
Species with Three P Atoms
transition is correctly assigned as the 2E′ r X2A2′ band system
of PO3. The new experimental work does not show any infrared
evidence for PO3, but we are able to identify bands associated
with PO2, PO2-, P2O, OPOPO, and O2PPO2. P4 is also observed
in experiment, but we are unable to observe any evidence for
the expected products such as P4O and P3O.
16O
18O
ω
I
ω
R(16/18)
P3O Rhombus (E ) 0.0 kcal/mol)
b1
b2
a1
a1
b2
a1
162
368
409
533
641
730
0
13
3
6
18
67
157
368
405
533
615
792
1.0307
1.0000
1.0109
1.0003
1.0413
1.0395
Acknowledgment. L.A. thanks the National Science Foun-
dation (Grant CHE 97-00116) for financial support.
References and Notes
OdPP2 (E ) 13.1 kcal/mol)
(1) Withnall, R.; Andrews, L. J. Phys. Chem. 1988, 92, 4610.
(2) Withnall, R.; McCluskey, M.; Andrews, L. J. Phys. Chem. 1989,
93, 126.
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(4) Lohr, L. L. J. Phys. Chem. 1984, 88, 5569. Lohr, L. L; Boehm, R.
C. J. Phys. Chem. 1987, 91, 3203. Lohr, L. L. J. Phys. Chem. 1990, 94,
1807. Lohr, L. L. J. Phys. Chem. 1992, 96, 119.
b1
b2
a1
b2
a1
a1
208
257
328
490
555
9
12
3
204
249
1.0189
1.0294
1.0045
1.0010
1.0125
1.0336
327
490
4
11
171
548
1213
1254
(5) Becke, A. D. J. Chem. Phys. 1993, 98, 5648.
(6) Stephens, P. J.; Devlin, F. J.; Chabalowski, C. F.; Frisch, M. J. J.
Phys. Chem. 1994, 98, 11623.
(7) Frisch, M. J.; Pople, J. A.; Binkley, J. S., J. Chem. Phys. 1984, 80,
3265 and references therein.
TABLE 12: B3LYP/6-31+G* Harmonic Frequencies (cm-1),
Intensities (km/mol), and 16O to 18O Isotopic Ratios for
Species with Four P Atoms and Zero or One Oxygena
(8) Stratmann, R. E.; Scuseria, G. E.; Frisch, M. J. J. Chem. Phys.
1998, 109, 8218.
(9) Bartlett, R. J. Annu. ReV. Phys. Chem. 1981, 32, 359.
(10) Raghavachari, K.; Trucks, G. W.; Pople, J. A.; Head-Gordon, M.
Chem. Phys. Lett. 1989, 157, 479.
16O
18O
ω
ω
I
R(16/18)
P4
e
t2
a1
365
0
5
0
(11) Gaussian 98, Revision A.6: M. J. Frisch, G. W. Trucks, H. B.
Schlegel, G. E. Scuseria, M. A. Robb, J. R. Cheeseman, V. G. Zakrzewski,
J. A. Montgomery, Jr., R. E. Stratmann, J. C. Burant, S. Dapprich, J. M.
Millam, A. D. Daniels, K. N. Kudin, M. C. Strain, O. Farkas, J. Tomasi,
V. Barone, M. Cossi, R. Cammi, B. Mennucci, C. Pomelli, C. Adamo, S.
Clifford, J. Ochterski, G. A. Petersson, P. Y. Ayala, Q. Cui, K. Morokuma,
D. K. Malick, A. D. Rabuck, K. Raghavachari, J. B. Foresman, J.
Cioslowski, J. V. Ortiz, B. B. Stefanov, G. Liu, A. Liashenko, P. Piskorz,
I. Komaromi, R. Gomperts, R. L. Martin, D. J. Fox, T. Keith, M. A. Al-
Laham, C. Y. Peng, A. Nanayakkara, C. Gonzalez, M. Challacombe, P. M.
W. Gill, B. Johnson, W. Chen, M. W. Wong, J. L. Andres, C. Gonzalez,
M. Head-Gordon, E. S. Replogle, and J. A. Pople, Gaussian, Inc., Pittsburgh,
PA, 1998.
(12) ACES II is a computational chemistry package especially designed
for coupled cluster and many body perturbation calculations. The SCF,
transformation, correlation energy, and gradient codes were written by J.
F. Stanton, J. Gauss, J. D. Watts, W. J. Lauderdale, and R. J. Bartlett. The
two-electron integrals are taken from the vectorized MOLECULE code of
J. Almlo¨f and P. R. Taylor. ACES II includes a modified version of the
ABACUS integral derivatives program, written by T. Helgaker, H. J. Jensen,
P. Jørensen, J. Olsen, and P. R. Taylor, and the geometry optimization and
vibrational analysis package written by J. F. Stanton and D. E. Bernholdt.
(13) Burkholder, T. R.; Andrews, L. J. Chem. Phys. 1991, 95, 8697.
(14) McCluskey, M.; Andrews, L. J. Phys. Chem. 1991, 95, 3545.
(15) Andrews, L.; Withnall, R. J. Am. Chem. Soc. 1988, 110, 5606.
(16) Andrews, L.; McCluskey, M.; Mielke, Z.; Withnall, R. J. Mol.
Struct. 1990, 222, 95.
461 (465.8)
604
P4O (Ring) (E ) 0.0 kcal/mol)
a2
b1
b2
a1
a1
a1
b2
a1
b2
207
297
313
426
458
521
550
620
768
0
6
2
207
286
312
418
454
521
550
604
734
1.0000
1.0394
1.0007
1.0183
1.0074
1.0002
1.0001
1.0266
1.0462
5
14
5
9
39
25
P4O (Edge) (E ) 12.7 kcal/mol)
b1
a1
a2
b1
a1
b2
a1
b2
a1
315
327
336
412
421
441
537
637
717
6
0
0
5
1
9
6
303
325
336
411
418
441
537
612
690
1.0386
1.0053
1.0000
1.0001
1.0073
1.0002
1.0007
1.0400
1.0394
35
68
OdPP3 (E ) 29.0 kcal/mol)
(17) Mielke, Z.; McCluskey, M.; Andrews, L. Chem. Phys. Lett. 1990,
165, 146.
(18) McCluskey, M.; Andrews, L. J. Phys. Chem. 1991, 95, 2988.
(19) Qian, H.-B.; Davis, P. B.; Hamilton, P. A. J. Chem. Soc., Faraday
Trans. 1995, 91, 2993.
(20) Xu, C.; de Beer, E.; Neumark, D. M. J. Chem. Phys. 1996, 104,
2749.
e
e
a1
e
a1
a1
228
323
397
496
548
26
0
222
323
393
496
543
1.0291
1.0000
1.0110
1.0008
1.0085
1.0330
0
18
0
183
1221
1182
(21) Illenberger, E. Ber. Bunsen-Ges. Phys. Chem. 1982, 86, 252;
Matejcik, S.; Kiendler, A.; Stamatovic, A.; Mark, T. D. Int. J. Mass.
Spectrom. Ion Processes. 1995, 149/150, 311.
a The relevant experimental bands from Table 4 are given in
parentheses for comparison.
(22) Zhou, M. F.; Andrews, L. J. Am. Chem. Soc. 1998, 120, 11499.
(23) Zhou, M. F.; Chertihin, G. V.; Andrews, L. J. Chem. Phys. 1998,
109, 10893.
V. Conclusions
(24) Zhou, M. F.; Andrews, L. J. Phys. Chem. A 1999, 103, 2964.
(25) Andrews, L. J. Chem. Phys. 1968, 48, 972.
(26) Jacox, M. E.; Milligan, D. E. J. Chem. Phys. 1971, 54, 3935.
(27) Prochaska, F. T.; Andrews, L. J. Chem. Phys. 1977, 67, 1091 and
references therein.
(28) Maier, G.; Reisenauer, H. P.; Hu, J.; Hess, B. A., Jr.; Schaad, L. J.
Tetrahedron Lett. 1989, 30, 4105.
(29) Zhou, M. F.; Andrews, L. J. Chem. Phys. 1999, 111, 6036.
(30) McCluskey, M.; Andrews, L. J. Phys. Chem. 1991, 95, 2679.
The computed frequencies and experiment suggest that the
band at 480.3 cm-1 should be reassigned to PO3-. The computed
results show that the related band at 1273.3 cm-1 also agrees
much better with PO3 than PO3. This reassignment is a clear
example of the synergistic effect of applying both theory and
experiment to the identification of IR bands.
-
The computed results also suggest that the observed electronic