When a Ne:H2:CO2=800:10:1 mixture is codeposited at 4.3 K with neon atoms that have been excited in a microwave discharge, the infrared spectrum of the resulting solid deposit includes not only absorptions characteristic of experiments from which H2 is absent, but also numerous product absorptions that are common to similar experiments on Ne:HCOOH samples. The carriers of these latter absorptions include HCOOH itself, as well as trans-HOCO, HCOOH+, and HCO2. Detailed isotopic substitution studies confirm the infrared identifications of HCOOH+ and HCO2 and permit the identification of two previously unassigned vibrational fundamentals each of HOCO+ and DOCO+. Density functional calculations for the latter species support the proposed assignments. Evidence is presented for the stabilization of the H2CO2 anion complex, in which the H2 moiety becomes infrared-active. The processes that result in the stabilization of these products are considered.

1.
M. E. Jacox, in Chemistry and Physics of Matrix Isolated Species, edited by L. Andrews and M. Moskovits (North-Holland, Amsterdam, 1989), p. 75.
2.
M. E.
Jacox
and
W. E.
Thompson
,
J. Chem. Phys.
91
,
1410
(
1989
).
3.
W. E.
Thompson
and
M. E.
Jacox
,
J. Chem. Phys.
91
,
3826
(
1989
);
M. E.
Jacox
and
W. E.
Thompson
,
J. Chem. Phys.
100
,
750
(
1994
).
4.
W. E.
Thompson
and
M. E.
Jacox
,
J. Chem. Phys.
93
,
3856
(
1990
).
5.
W. E.
Thompson
and
M. E.
Jacox
,
J. Chem. Phys.
95
,
735
(
1991
).
6.
M.
Zhou
and
L.
Andrews
,
J. Chem. Phys.
110
,
6820
(
1999
).
7.
W. E.
Thompson
and
M. E.
Jacox
,
J. Chem. Phys.
111
,
4487
(
1999
).
8.
M. E.
Jacox
and
W. E.
Thompson
,
J. Phys. Chem.
95
,
2781
(
1991
).
9.
Certain commercial instruments and materials are identified in this paper in order to specify adequately the experimental procedure. In no case does such identification imply a recommendation or endorsement by the National Institute of Standards and Technology, nor does it imply that the instruments or materials identified are necessarily the best available for the purpose.
10.
D.
Forney
,
W. E.
Thompson
, and
M. E.
Jacox
,
J. Chem. Phys.
97
,
1664
(
1992
).
11.
M. E.
Jacox
and
W. B.
Olson
,
J. Chem. Phys.
86
,
3134
(
1987
).
12.
D.
Forney
,
M. E.
Jacox
, and
W. E.
Thompson
,
J. Chem. Phys.
119
,
10814
(
2003
), preceding paper.
13.
Tables numbered starting with the letter E are found in the electronic archives, but not in the printed text. See EPAPS Document No. E-JCPSA6-119-016344 for Tables E-1 to E-6, concerned with summaries of the experimental data, with the rotational constants of unenriched hydroxyformyl cation, and with the positions and intensities of the vibrational fundamentals of selected isotopomers of that species, obtained from B3LYP calculations conducted as a part of the present study.
A direct link to this document may be found in the online article’s HTML reference section. The document may also be reached via the EPAPS homepage (http://www.aip.org/pubservs/epaps.html) or from ftp.aip.org in the directory /epaps/. See the EPAPS homepage for more information.
14.
T.
Amano
and
K.
Tanaka
,
J. Chem. Phys.
82
,
1045
(
1985
);
T.
Amano
and
K.
Tanaka
,
J. Chem. Phys.
83
,
3721
(
1985
).
15.
M.
Bogey
,
C.
Demuynck
, and
J.-L.
Destombes
,
J. Chem. Phys.
84
,
10
(
1986
).
16.
P.
Thaddeus
,
M.
Guelin
, and
R. A.
Linke
,
Astrophys. J. Lett.
246
,
L41
(
1981
).
17.
M. J.
Frisch
,
H. F.
Schaefer
III
, and
J. S.
Binkley
,
J. Phys. Chem.
89
,
2192
(
1985
).
18.
J. S.
Francisco
,
J. Chem. Phys.
107
,
9039
(
1997
).
19.
D.
Forney
,
M. E.
Jacox
,
C. L.
Lugez
, and
W. E.
Thompson
,
J. Chem. Phys.
115
,
8418
(
2001
).
20.
M. J. Frisch, G. W. Trucks, H. B. Schlegel et al., GAUSSIAN 98, Revision A.7, Gaussian, Inc., Pittsburgh, PA, 1998.
21.
A. D.
Becke
,
J. Chem. Phys.
98
,
5648
(
1993
);
C.
Lee
,
W.
Yang
, and
R. G.
Parr
,
Phys. Rev. B
37
,
785
(
1988
).
22.
T. H.
Dunning
,
J. Chem. Phys.
90
,
1007
(
1989
).
23.
M.
Bogey
,
C.
Demuynck
,
J.-L.
Destombes
, and
A.
Krupnov
,
J. Mol. Struct.
190
,
465
(
1988
).
24.
O.
Dopfer
,
R. V.
Olkhov
,
D.
Roth
, and
J. P.
Maier
,
Chem. Phys. Lett.
296
,
585
(
1998
).
25.
S. A.
Nizkorodov
,
O.
Dopfer
,
T.
Ruchti
,
M.
Meuwly
,
J. P.
Maier
, and
E. J.
Bieske
,
J. Phys. Chem.
99
,
17118
(
1995
).
26.
B.
Ruscic
,
M.
Schwarz
, and
J.
Berkowitz
,
J. Chem. Phys.
91
,
6780
(
1989
).
27.
B.
Ruscic
and
M.
Litorja
,
Chem. Phys. Lett.
316
,
45
(
2000
).
28.
K. P. Huber and G. Herzberg, Molecular Spectra and Molecular Structure. IV. Constants of Diatomic Molecules (Van Nostrand Reinhold, New York, 1979).
29.
J. A.
Nichols
,
R. A.
Kendall
,
S. J.
Cole
, and
J.
Simons
,
J. Phys. Chem.
95
,
1074
(
1991
);
S. E.
Bradforth
,
D. W.
Arnold
,
D. M.
Neumark
, and
D. E.
Manolopoulos
,
J. Chem. Phys.
99
,
6345
(
1993
);
D. E.
Manolopoulos
,
K.
Stark
,
H. J.
Werner
,
D. W.
Arnold
,
S. E.
Bradforth
, and
D. M.
Neumark
,
Science
262
,
1852
(
1993
);
A. I.
Boldyrev
,
J.
Simons
,
G. V.
Mil’nikov
,
V. A.
Benderskii
,
S. Y.
Grebenshchikov
, and
E. V.
Vetoshkin
,
J. Chem. Phys.
102
,
1295
(
1995
).
30.
D. A.
Wild
,
R. L.
Wilson
,
P. S.
Weiser
, and
E. J.
Bieske
,
J. Chem. Phys.
113
,
10154
(
2000
);
D. A.
Wild
,
P. S.
Weiser
,
E. J.
Bieske
, and
A.
Zehnacker
,
J. Chem. Phys.
115
,
824
(
2001
).
31.
D. A.
Wild
,
P. S.
Weiser
, and
E. J.
Bieske
,
J. Chem. Phys.
115
,
6394
(
2001
);
D. A.
Wild
,
Z. M.
Loh
,
R. L.
Wilson
, and
E. J.
Bieske
,
J. Chem. Phys.
117
,
3256
(
2002
).
32.
D.
Shiner
,
J. M.
Gilligan
,
B. M.
Cook
, and
W.
Lichten
,
Phys. Rev. A
47
,
4042
(
1993
).
33.
C. F.
Batten
,
J. A.
Taylor
, and
G. G.
Meisels
,
J. Chem. Phys.
65
,
3316
(
1976
).
34.
R.
Frey
,
B.
Gotchev
,
O. F.
Kalman
,
W. B.
Peatman
,
H.
Pollak
, and
E. W.
Schlag
,
Chem. Phys.
21
,
89
(
1977
).
35.
A. W.
Potts
and
G. H.
Fattahallah
,
J. Phys. B
13
,
2545
(
1980
);
L.
Wang
,
J. E.
Reutt
,
Y. T.
Lee
, and
D. A.
Shirley
,
J. Electron Spectrosc. Relat. Phenom.
47
,
167
(
1988
).
36.
K.-M.
Weitzel
,
J.
Mahnert
, and
M.
Penno
,
Chem. Phys. Lett.
224
,
371
(
1994
).
37.
P. L.
Kronebusch
and
J.
Berkowitz
,
Int. J. Mass Spectrom. Ion Phys.
22
,
283
(
1976
).
38.
T.
McAllister
and
P.
Pitman
,
Int. J. Mass Spectrom. Ion Phys.
19
,
423
(
1976
);
G. B.
Scott
,
D. A.
Fairley
,
C. G.
Freeman
,
M. J.
McEwan
,
P.
Spanel
, and
D.
Smith
,
J. Chem. Phys.
106
,
3982
(
1997
).
39.
E.
Uggerud
,
W.
Koch
, and
H.
Schwarz
,
Int. J. Mass Spectrom. Ion Processes
73
,
187
(
1986
);
P. J. A.
Ruttink
and
P. C.
Burgers
,
Int. J. Mass Spectrom. Ion Processes
113
,
23
(
1992
).
40.
D.
Forney
,
M. E.
Jacox
, and
W. E.
Thompson
,
J. Chem. Phys.
98
,
841
(
1993
).
41.
G. C.
Schatz
,
M. S.
Fitzcharles
, and
L. B.
Harding
,
Faraday Discuss. Chem. Soc.
84
,
359
(
1987
);
K.
Kudla
,
G. C.
Schatz
, and
A. F.
Wagner
,
J. Chem. Phys.
95
,
1635
(
1991
);
K. S.
Bradley
and
G. C.
Schatz
,
J. Chem. Phys.
106
,
8464
(
1997
).
42.
A.
Pelc
,
W.
Sailer
,
P.
Scheier
,
M.
Probst
,
N. J.
Mason
,
E.
Illenberger
, and
T. D.
Märk
,
Chem. Phys. Lett.
361
,
277
(
2002
).
43.
P. C.
Burgers
,
J. L.
Holmes
, and
J. E.
Szulejko
,
Int. J. Mass Spectrom. Ion Processes
57
,
159
(
1984
).
44.
T. G.
Clements
,
R. E.
Continetti
, and
J. S.
Francisco
,
J. Chem. Phys.
117
,
6478
(
2002
).
45.
H.
Drexel
,
G.
Senn
,
T.
Fiegele
,
P.
Scheier
,
A.
Stamatovic
,
N. J.
Mason
, and
T. D.
Märk
,
J. Phys. B
34
,
1415
(
2001
).
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