Infrared spectra in the C–H stretch region are reported for the allyl (CH2CHCH2) and allyl peroxy (CH2=CH–CH2OO·) radicals solvated in superfluid helium nanodroplets. Nine bands in the spectrum of the allyl radical have resolved rotational substructure. We have assigned three of these to the ν1 (a1), ν3 (a1), and ν13 (b2) C–H stretch bands and four others to the ν14/(ν15+2ν11) (b2) and ν2/(ν4+2ν11) (a1) Fermi dyads, and an unassigned resonant polyad is observed in the vicinity of the ν1 band. Experimental coupling constants associated with Fermi dyads are consistent with quartic force constants obtained from density functional theory computations. The peroxy radical was formed within the He droplet via the reaction between allyl and O2 following the sequential pick-up of the reactants. Five stable conformers are predicted for the allyl peroxy radical, and a computed two-dimensional potential surface for rotation about the CC–OO and CC–CO bonds reveals multiple isomerization barriers greater than ≈300 cm−1. Nevertheless, the C–H stretch infrared spectrum is consistent with the presence of a single conformer following the allyl + O2 reaction within helium droplets.
REFERENCES
1.
J. A.
Miller
and C. F.
Melius
, Combust. Flame
91
, 21
(1992
).2.
A.
D’Anna
, A.
Violi
, and A.
D’Alessio
, Combust. Flame
121
, 418
(2000
).3.
J. A.
Miller
and S. J.
Klippenstein
, J. Phys. Chem. A
105
, 7254
(2001
).4.
H.
Richter
and J. B.
Howard
, Phys. Chem. Chem. Phys.
4
, 2038
(2002
).5.
M.
Frenklach
, Phys. Chem. Chem. Phys.
4
, 2028
(2002
).6.
J. A.
Miller
, M. J.
Pilling
, and J.
Troe
, Proc. Combust. Inst.
s30
, 43
(2005
).7.
Y.
Georgievskii
, J. A.
Miller
, and S. J.
Klippenstein
, Phys. Chem. Chem. Phys.
9
, 4259
(2007
).8.
J. A.
Miller
, S. J.
Klippenstein
, Y.
Georgievskii
, L. B.
Harding
, W. D.
Allen
, and A. C.
Simmonett
, J. Phys. Chem. A
114
, 4881
(2010
).9.
G. B.
Ellison
, G. E.
Davico
, V. M.
Bierbaum
, and C. H.
DePuy
, Int. J. Mass Spectrom.
156
, 109
(1996
).10.
J.
Lee
and J. W.
Bozzelli
, Proc. Combust. Inst.
30
, 1015
(2005
).11.
T. M.
Selby
, G.
Meloni
, F.
Goulay
, S. R.
Leone
, A.
Fahr
, C. A.
Taatjes
, and D. L.
Osborn
, J. Phys. Chem. A
112
, 9366
(2008
).12.
M. P.
Rissanen
, D.
Amedro
, A. J.
Eskola
, T.
Kurten
, and R. S.
Timonen
, J. Phys. Chem. A
116
, 3969
(2012
).13.
S.
Nandi
, P. A.
Arnold
, B. K.
Carpenter
, M. R.
Nimlos
, D. C.
Dayton
, and G. B.
Ellison
, J. Phys. Chem. A
105
, 7514
(2001
).14.
J. X.
Han
, Y. G.
Utkin
, H. B.
Chen
, N. T.
Hunt
, and R. F.
Curl
, J. Chem. Phys.
116
, 6505
(2002
).15.
D.
Uy
, S.
Davis
, and D. J.
Nesbitt
, J. Chem. Phys.
109
, 7793
(1998
).16.
E.
Hirota
, C.
Yamada
, and M.
Okunishi
, J. Chem. Phys.
97
, 2963
(1992
).17.
P. S.
Thomas
and T. A.
Miller
, Chem. Phys. Lett.
491
, 123
(2010
).18.
E.
Knuth
, B.
Schilling
, and J. P.
Toennies
, in Proceedings of the 19th International Symposium on Rarefied Gas Dynamics
(Oxford University Press
, London
, 1995
).19.
M.
Lewerenz
, B.
Schilling
, and J. P.
Toennies
, Chem. Phys. Lett.
206
, 381
(1993
).20.
J.
Küpper
, J. M.
Merritt
, and R. E.
Miller
, J. Chem. Phys.
117
, 647
(2002
).21.
C. P.
Moradi
, A. M.
Morrison
, S. J.
Klippenstein
, C. F.
Goldsmith
, and G. E.
Douberly
, “The propargyl + O2 reaction in helium droplets: entrance barrier or not
?” J. Phys. Chem. A
(2013
).22.
M.
Lewerenz
, B.
Schilling
, and J. P.
Toennies
, J. Chem. Phys.
102
, 8191
(1995
).23.
D. M.
Brink
and S.
Stringari
, Z. Phys. D: At., Mol. Clusters
15
, 257
(1990
).24.
M.
Hartmann
, R. E.
Miller
, J. P.
Toennies
, and A.
Vilesov
, Phys. Rev. Lett.
75
, 1566
(1995
).25.
R. P.
Ruiz
, K. D.
Bayes
, M. T.
Macpherson
, and M. J.
Pilling
, J. Phys. Chem.
85
, 1622
(1981
).26.
C. A.
Morgan
, M. J.
Pilling
, J. M.
Tulloch
, R. P.
Ruiz
, and K. D.
Bayes
, J. Chem. Soc., Faraday Trans. 2
78
, 1323
(1982
).27.
I. R.
Slagle
, E.
Ratajczak
, M. C.
Heaven
, D.
Gutman
, and A. F.
Wagner
, J. Am. Chem. Soc.
107
, 1838
(1985
).28.
J. W.
Bozzelli
and A. M.
Dean
, J. Phys. Chem.
97
, 4427
(1993
).29.
A. M.
Morrison
, T.
Liang
, and G. E.
Douberly
, Rev. Sci. Instrum.
84
, 013102
(2013
).30.
S. A.
Chin
and E.
Krotscheck
, Phys. Rev. B
52
, 10405
(1995
).31.
M. J.
Frisch
, G. W.
Trucks
, H. B.
Schlegel
et al., GAUSSIAN 09, Revision A.01, Gaussian, Inc., Wallingford, CT, 2009
.32.
V.
Barone
, J. Chem. Phys.
122
, 014108
(2005
).33.
J.
Bloino
and V.
Barone
, J. Chem. Phys.
136
, 124108
(2012
).34.
L. A.
Curtiss
, K.
Raghavachari
, G. W.
Trucks
, and J. A.
Pople
, J. Chem. Phys.
94
, 7221
(1991
).35.
H.
Buchenau
, J. P.
Toennies
, and J. A.
Northby
, J. Chem. Phys.
95
, 8134
(1991
).36.
J. D.
DeSain
, R. I.
Thompson
, S. D.
Sharma
, and R. F.
Curl
, J. Chem. Phys.
109
, 7803
(1998
).37.
M. P.
Rissanen
, D.
Amedro
, L.
Krasnoperov
, P.
Marshall
, and R. S.
Timonen
, J. Phys. Chem. A
117
, 793
(2013
).38.
C.
Callegari
, K. K.
Lehmann
, R.
Schmied
, and G.
Scoles
, J. Chem. Phys.
115
, 10090
(2001
).39.
J. P.
Toennies
and A. F.
Vilesov
, Angew. Chem., Int. Ed.
43
, 2622
(2004
).40.
M. Y.
Choi
, G. E.
Douberly
, T. M.
Falconer
, W. K.
Lewis
, C. M.
Lindsay
, J. M.
Merritt
, P. L.
Stiles
, and R. E.
Miller
, Int. Rev. Phys. Chem.
25
, 15
(2006
).41.
F.
Dong
, S.
Davis
, and D. J.
Nesbitt
, J. Phys. Chem. A
110
, 3059
(2006
).42.
D. S.
Skvortsov
and A. F.
Vilesov
, J. Chem. Phys.
130
, 151101
(2009
).43.
A.
Lindinger
, J. P.
Toennies
, and A. F.
Vilesov
, J. Chem. Phys.
110
, 1429
(1999
).44.
M. Y.
Choi
, F.
Dong
, and R. E.
Miller
, Philos. Trans. R. Soc. London, Ser. A
363
, 393
(2005
).45.
M. Y.
Choi
and R. E.
Miller
, J. Am. Chem. Soc.
128
, 7320
(2006
).46.
K.
Nauta
and R. E.
Miller
, J. Chem. Phys.
115
, 10138
(2001
).47.
G. E.
Douberly
and R. E.
Miller
, J. Phys. Chem. B
107
, 4500
(2003
).48.
G. E.
Douberly
and R. E.
Miller
, J. Chem. Phys.
122
, 024306
(2005
).49.
A.
Metzelthin
, E.
Sanchez-Garcia
, O.
Birer
, G.
Schwaab
, W.
Thiel
, W.
Sander
, and M.
Havenith
, ChemPhysChem
12
, 2009
(2011
).50.
H.
Forbert
, M.
Masia
, A.
Kaczmarek-Kedziera
, N. N.
Nair
, and D.
Marx
, J. Am. Chem. Soc.
133
, 4062
(2011
).51.
D.
Pentlehner
, C.
Greil
, B.
Dick
, and A.
Slenczka
, J. Chem. Phys.
133
, 114505
(2010
).52.
P. L.
Raston
, T.
Liang
, and G. E.
Douberly
, J. Chem. Phys.
137
, 184302
(2012
).53.
P. L.
Raston
, J.
Agarwal
, J. M.
Turney
, H. F.
Schaefer
, and G. E.
Douberly
, J. Chem. Phys.
138
, 194303
(2013
).54.
P. L.
Raston
, T.
Liang
, and G. E.
Douberly
, J. Chem. Phys.
138
, 174302
(2013
).© 2013 AIP Publishing LLC.
2013
AIP Publishing LLC
You do not currently have access to this content.
