Four isotopes of the methanol cation radical (CH3OH+) have been generated by three independent methods and isolated in neon matrices at 4 K for a detailed electron spin resonance (ESR) investigation. The ion generation methods employed were X irradiation, photoionization, and electron ionization. The nuclear hyperfine (A tensors) measurements were compared with those obtained from ab initio extended basis set multireference configuration interaction (CI) wave functions. The relationships between geometry and electronic structures were fully explored. The trend in the large isotropic methyl hydrogen A values for the isoelectronic series CH3F+, CH3OH+, and CH3NH2+ was found to follow the trend in dissociation energies for these radical cations. The neon magnetic parameters for CH3OH+ are gx=2.0036(4) and gz=2.010(1); Aiso (methyl hydrogens)=229(1) MHz, ‖Ax‖=54(2) and ‖Az‖=80(3) MHz for the hydroxy hydrogen; ‖Ax‖=40(2) and ‖Az‖=29(4) MHz for 13C. The observed magnetic parameters for CH2DOH+ indicate an unusually large deuterium effect Aiso (CH2)=329 MHz with ‖Aiso‖=4.1(3) MHz for the methyl deuterium. These results show that averaging of the methyl hydrogen environments is occurring on the ESR time scale.
REFERENCES
1.
(a)
J.
Mangum
, A.
Wooten
, R.
Loren
, and E.
Wadiak
, Astrophys. J.
348
, 542
(1990
);(b)
R. L.
Plambeck
and M. C. H.
Wright
, Astrophys. J.
330
, L61
(1988
)., Astrophys. J.
2.
E. M.
Bramer
, E.
Weger
, J.
Ischtwan
, W. A.
Brand
, and K.
Levsen
, Int. J. Mass. Spectrom. Ion Proc.
55
, 83
(1983
).3.
M. B.
Robin
and N. A.
Kuebler
, J. Electron Spectrosc. Relat. Phenom.
1
, 13
(1972
);K. A. G.
Macneil
and R. N.
Dixon
, J. Electron Spectrosc. Relat. Phenom.
11
, 315
(1977
); , J. Electron Spectrosc. Relat. Phenom.
C.
Utsunomiya
, T.
Kobayashi
, and S.
Nagakura
, Bull. Chem. Soc. Jpn.
53
, 1216
(1980
).4.
T.
Momose
, Y.
Endo
, E.
Hirota
, and T.
Shida
, J. Chem. Phys.
88
, 5338
(1988
); , J. Chem. Phys.
T.
Momose
, Y.
Endo
, E.
Hirota
, and T.
Shida
, 90
, 4636
(1989
)., J. Chem. Phys.
5.
D. K.
Russell
and H. E.
Radford
, J. Chem. Phys.
72
, 2750
(1980
)., J. Chem. Phys.
6.
7.
H.
Kubodera
, T.
Shida
, and K.
Shimokoshi
, J. Phys. Chem.
85
, 2583
(1981
).8.
L. B.
Knight
, Jr., B. W.
Gregory
, D. W.
Hill
, and C. A.
Arrington
, J. Chem. Phys.
94
, 67
(1991
).9.
C. J.
Maxwell
, F. B. C.
Machado
, and E. R.
Davidson
, J. Am. Chem. Soc.
114
, 6496
(1992
).10.
M.
Iwasaki
, K.
Toriyama
, and K.
Nunome
, Chem. Phys. Lett.
111
, 309
(1984
).11.
L. B.
Knight
, Jr., J.
Steadman
, D.
Feller
, and E. R.
Davidson
, J. Am. Chem. Soc.
106
, 3700
(1984
).12.
13.
(a) L. B. Knight, Jr., in Radical Ionic Systems, edited by A. Lund and M. Shiotani (Kluwer Academic, Dordrecht, 1991), pp. 73–97;
(b) L. B. Knight, Jr., in Chemistry and Physics of Matrix-Isolated Species, edited by L. Andrews and M. Moskovits (North-Holland, Amsterdam, 1989), Chap. 7.
14.
A. C.
Legou
, Faraday Discuss. Chem. Soc.
86
, 1
(1988
). Both volumes discuss radicals in condensed phases., Faraday Discuss. Chem. Soc.
15.
S. E.
Strahan
, R. P.
Mueller
, and R. J.
Saykally
, J. Chem. Phys.
85
, 1252
(1986
).16.
(a)
N. D.
Piltch
, P. G.
Szanto
, T. G.
Anderson
, C. S.
Gudeman
, T. A.
Dixon
, and R. C.
Woods
, J. Chem. Phys.
76
, 3385
(1982
);(b)
A.
Carrington
, D. R. J.
Milverton
, and P. J.
Sarre
, Mol. Phys.
35
, 1505
(1978
).17.
(a)
S. D.
Rosner
, T. D.
Gaily
, and R. A.
Holt
, J. Mol. Spectrosc.
109
, 73
(1985
);(b)
N. B.
Mansour
, C.
Kurtz
, T. C.
Steimle
, G. L.
Goodman
, L.
Young
, T. J.
Scholl
, S. D.
Rosner
, and R. A.
Holt
, Phys Rev. A
44
, 4418
(1991
).18.
W. Weltner, Jr., Magnetic Atoms and Molecules (Van Nostrand-Reinhold, New York, 1983).
19.
20.
L. B.
Knight
, Jr., M.
Winiski
, P.
Kudelko
, and C. A.
Arrington
, J. Chem. Phys.
91
, 3368
(1989
).21.
T. Bally, Radical Ionic Systems, edited by A. Lund and M. Shiotani (Kluwer Academic, Dordrecht, 1991), pp. 3–52;
T.
Shida
, E.
Hasel-back
, and T.
Bally
, Acc. Chem. Res.
17
, 180
(1984
);K.
Toriyama
, K.
Nunome
, and M.
Isasaki
, J. Chem. Phys.
77
, 5891
(1982
).22.
23.
24.
25.
L. B.
Knight
, Jr., J. O.
Herlong
, R.
Babb
, E.
Earl
, D. W.
Hill
, and C. A.
Arrington
, J. Phys. Chem.
95
, 2732
(1991
).26.
L. B.
Knight
, Jr., S. T.
Cobranchi
, and E.
Earl
, J. Chem. Phys.
88
, 7348
(1988
).27.
L. B.
Knight
, Jr., S. T.
Cobranchi
, J.
Herlong
, T.
Kirk
, K.
Balasubramanian
, and K. K.
Das
, J. Chem. Phys.
92
, 2721
(1990
).28.
L. B.
Knight
, Jr., D. W.
Hill
, T. J.
Kirk
, and C. A.
Arrington
, J. Phys. Chem.
96
, 555
(1992
).29.
L. B.
Knight
, Jr., J. O.
Herlong
, T. J.
Kirk
, and C. A.
Arrington
, J. Chem. Phys.
96
, 5604
(1992
).30.
D. Feller and E. R. Davidson, in Theoretical Models of Chemical Bonding, edited by Z. B. Masksic (Springer, Berlin, 1991).
31.
D. M.
Chipman
, I.
Carmichael
, and D.
Feller
, J. Phys. Chem.
95
, 4702
(1991
).32.
33.
34.
35.
W. J. Hehre, L. Radom, P. v.R. Schleye, and J. Pople, in Ab Initio Molecular Orbital Theory (Wiley, New York, 1986).
36.
37.
L. B.
Knight
, Jr., S. T.
Cobranchi
, J. T.
Petty
, E.
Earl
, D.
Feller
, and E. R.
Davidson
, J. Chem. Phys.
90
, 690
(1989
).38.
L. B.
Knight
, Jr., A.
Ligon
, R. W.
Woodward
, D.
Feller
, and E. R.
Davidson
, J. Am. Chem. Soc.
107
, 2857
(1985
).39.
B. F.
Yates
, W. J.
Bouma
, and L.
Radom
, J. Am. Chem. Soc.
109
, 2250
(1987
).40.
L. B.
Knight
,Jr. , E.
Earl
, A. R.
Ligon
, D. P.
Cobranchi
, J. R.
Woodward
, J. M.
Bostick
, E. R.
Davidson
, and D.
Feller
, J. Am. Chem. Soc.
108
, 5065
(1986
);L. B.
Knight
, Jr., A.
Ligon
, S. T.
Cobranchi
, D. P.
Cobranchi
, E.
Earl
, D.
Feller
, and E. R.
Davidson
, J. Chem. Phys.
85
, 5437
(1986
).41.
42.
43.
L. B.
Knight
, Jr., M.
Winiski
, P.
Miller
, C. A.
Arrington
, and D.
Feller
, J. Chem. Phys.
91
, 4468
(1989
).44.
M. J. Frisch, M. Head-Gordon, G. W. Tucks, J. B. Forseman, H. B. Schlegel, K. Raghavachari, M. Robb, J. S. Binkley, C. Gonzalez, D. J. Defrees, D. J. Fox, R. A. Whitehead, R. Seeger, C. F. Melius, J. Baker, R. L. Martin, L. R. Kahn, J. J. P. Stewart, S. Topiol, and J. A. Pople, GAUSSIAN 90, revision G, Gaussian, Inc., Pittsburgh, PA 1990.
45.
J. S.
Binkley
, J. A.
Pople
, and W. J.
Hehre
, J. Am. Chem. Soc.
102
, 939
(1980
).46.
W. H.
Hehre
, R.
Ditchfield
, and J. A.
Pople
, J. Chem. Phys.
56
, 2257
(1972
).47.
M. Dupuis, D. Spangler, and J. J. Wendoloski, National Resource for Computations in Chemistry Software Catalog (University of California, Berkeley, CA, 1980), program QG01.
This version due to
M. W.
Schmidt
, K. K.
Baldridge
, J. A.
Boatz
, J. H.
Jensen
, S.
Koseki
, M. S.
Gordon
, K. A.
Nguyen
, T. L.
Windus
, and S. T.
Elbert
, QCPE Bull.
10
, 52
(1990
).48.
M. J.
Frisch
, J. A.
Pople
, and J. S.
Binkley
, J. Chem. Phys.
80
, 3265
(1984
).49.
J. A.
Pople
, M.
Head-Gordon
, and K.
Raghavachari
, J. Chem. Phys.
90
, 4635
(1989
).50.
K.
Raghavachari
, G. W.
Tucks
, J. A.
Pople
, and M.
Head-Gordon
, Chem. Phys. Lett.
157
, 479
(1989
).51.
MELDF-X was originally written by L. McMurchie, S. Elbert, S. Lang-hoif, and E. R. Davidson. It has been modified substantially by D. Feller, R. Cave, D. Rawlings, R. Frey, R. Daasch, L. Nitzche, P. Phillips, K. Iberle, C. Jackels, and E. R. Davidson.
52.
53.
54.
55.
56.
E. L.
Cochran
, F. J.
Adrian
, and V. A.
Bowers
, J. Chem. Phys.
40
, 213
(1964
).57.
58.
A. K.
Koh
and D. J.
Miller
, At. Data Nucl. Data Tables
33
, 235
(1985
).
This content is only available via PDF.
© 1992 American Institute of Physics.
1992
American Institute of Physics
You do not currently have access to this content.
