We calculate the standard state entropy, heat capacity, enthalpy, and Gibbs free energy for 13 radicals important for the combustion chemistry of biofuels. These thermochemical quantities are calculated from recently proposed methods for calculating partition functions of complex molecules by taking into account their multiple conformational structures and torsional anharmonicity. The radicals considered in this study are those obtained by hydrogen abstraction from 1-butanol, 2-methyl-1-propanol, and butanal. Electronic structure calculations for all conformers of the radicals were carried out using both density functional theory and explicitly correlated coupled cluster theory with quasipertubative inclusion of connected triple excitations. The heat capacity and entropy results are compared with sparsely available group additivity data, and trends in enthalpy and free energy as a function of radical center are discussed for the isomeric radicals.
REFERENCES
1.
J.
Zheng
, T.
Yu
, E.
Papajak
, I. M.
Alecu
, S. L.
Mielke
, and D. G.
Truhlar
, Phys. Chem. Chem. Phys.
13
, 10885
(2011
).2.
J.
Zheng
, T.
Yu
, and D. G.
Truhlar
, Phys. Chem. Chem. Phys.
13
, 19318
(2011
).3.
T.
Yu
, J.
Zheng
, and D. G.
Truhlar
, Phys. Chem. Chem. Phys.
14
, 482
(2011
).4.
J.
Zheng
and D. G.
Truhlar
, “Multi-path variational transition state theory for chemical reaction rates of complex polyatomic species: Ethanol + OH reactions
,” Faraday Discuss.
(published online).5.
P.
Seal
, E.
Papajak
, T.
Yu
, and D. G.
Truhlar
, J. Chem. Phys.
136
, 034306
(2012
).6.
P.
Seal
, E.
Papajak
, J.
Zheng
, and D. G.
Truhlar
, J. Phys. Chem. Lett.
3
, 264
(2012
).7.
T.
Yu
, J.
Zheng
, and D. G.
Truhlar
, Chem. Sci.
2
, 2199
(2011
).8.
T.
Yu
, J.
Zheng
, and D. G.
Truhlar
, J. Phys. Chem. A
116
, 297
(2012
).9.
X.
Xu
, E.
Papajak
, J.
Zheng
, and D. G.
Truhlar
, Phys. Chem. Chem. Phys.
14
, 4204
(2012
).10.
J.
Platt
, J. Chem. Phys.
15
, 419
(1947
).11.
J.
Platt
, J. Phys. Chem.
56
, 328
(1952
).12.
J.
Greenshields
and F.
Rossini
, J. Phys. Chem.
62
, 271
(1958
).13.
G.
Somayajulu
and B.
Zwolinski
, Trans. Faraday Soc.
62
, 2327
(1966
).14.
T.-P.
Thinh
, J.-L.
Duran
, and R.
Ramalho
, Ind. Eng. Chem. Process Des. Dev.
10
, 576
(1971
).15.
T.-P.
Thinh
and T.
Trong
, Can. J. Chem.
54
, 344
(1976
).16.
R.
Joshi
, J. Macromol. Sci., Chem.
4
, 1819
(1970
).17.
18.
N.
Cohen
and S.
Benson
, Chem. Rev.
93
, 2419
(1993
).19.
N.
Cohen
, J. Phys. Chem. Ref. Data
25
, 1411
(1996
).20.
T. H.
Lay
and J. W.
Bozzelli
, J. Phys. Chem. A
101
, 9505
(1997
).21.
N.
Sebbar
, J. W.
Bozzelli
, and H.
Bockhorn
, J. Phys. Chem. A
108
, 8353
–8366
(2004
).22.
H.
O’Neal
and S.
Benson
, in Free Radicals
, edited by J. K.
Kochi
(Wiley
, New York
, 1973
), pp. 275
.23.
T.
Ni
, R.
Caldwell
, and L.
Melton
, J. Am. Chem. Soc.
111
, 457
(1989
).24.
N.
Cohen
, J. Phys. Chem.
96
, 9052
(1992
).25.
M. K.
Sabbe
, F.
De Vieeschower
, M.-F.
Reyniers
, M.
Waroquier
, and G. B.
Marin
, J. Phys. Chem. A
112
, 12235
(2008
).26.
V. V.
Turovtsev
, Y. D.
Orlov
, and Y. A.
Lebedev
, Russ. J. Phys. Chem.
83
, 245
(2009
).27.
I.
Marsi
, B.
Viskolcz
, and L.
Seres
, J. Phys. Chem. A
104
, 4497
(2000
).28.
S. S.
Khan
, X.
Yu
, J. R.
Wade
, D.
Malmgren
, and L. J.
Broadbelt
, J. Phys. Chem.
113
, 5176
(2009
).29.
M. K.
Sabbe
, M.
Saeys
, M.-F.
Reyniers
, and G. B.
Marin
, J. Phys. Chem. A
109
, 7466
(2005
)30.
J. M.
Hudzik
and J. W.
Bozzelli
, J. Phys. Chem. A
114
, 7984
(2010
).31.
M. J.
Frisch
, G. W.
Trucks
, H. B.
Schlegel
et al., GAUSSIAN 09, Revision A.02, Gaussian, Inc., Wallingford, CT, 2009
.32.
Z.
Zhao
, R.
Peverati
, K.
Yang
, and D. G.
Truhlar
, mn-gfm version 5.2 computer program module, University of Minnesota, Minneapolis, 2011
.33.
Y.
Zhao
, N. E.
Schultz
, and D. G.
Truhlar
, J. Chem. Theory Comput.
4
, 1849
(2008
).34.
B. J.
Lynch
, Y.
Zhao
, and D. G.
Truhlar
, J. Phys. Chem. A
107
, 1384
(2003
).35.
T. H.
Dunning
Jr., J. Chem. Phys.
90
, 1007
(1989
).36.
R. A.
Kendall
, T. H.
Dunning
Jr., and R. J.
Harrison
, J. Chem. Phys.
96
, 6796
(1992
).37.
E.
Papajak
, H. R.
Leverentz
, J.
Zheng
, and D. G.
Truhlar
, J. Chem. Theory Comput.
5
, 1197
(2009
);
[PubMed]
E.
Papajak
, H. R.
Leverentz
, J.
Zheng
, and D. G.
Truhlar
, J. Chem. Theory Comput.
5
, 3330
(2009
).
[PubMed]
38.
E.
Papajak
and D. G.
Truhlar
, J. Chem. Theory Comput.
6
, 597
(2010
).39.
R.
Krishnan
, J. S.
Binkley
, R.
Seeger
, and J. A.
Pople
, J. Chem. Phys.
72
, 650
(1980
);T.
Clark
, J.
Chandrasekhar
, G. W.
Spitznagel
, and P. v. R.
Schleyer
, J. Comp. Chem.
4
, 294
(1983
);M. J.
Frisch
, J. A.
Pople
, and J. S.
Binkley
, J. Chem. Phys.
80
, 3265
(1984
).40.
I. M.
Alecu
, J.
Zheng
, Y.
Zhao
, and D. G.
Truhlar
, J. Chem. Theory Comput.
6
, 2872
(2010
).41.
G.
Knizia
, T. B.
Adler
, and H.-J.
Werner
, J. Chem. Phys.
130
, 054104
(2009
).42.
E.
Papajak
and D. G.
Truhlar
, J. Chem. Theory Comput.
7
, 10
(2011
).43.
E.
Papajak
, J.
Zheng
, X.
Xu
, H. R.
Leverentz
, and D. G.
Truhlar
, J. Chem. Theory Comput.
7
, 3027
(2011
).44.
W.
Kutzelnigg
, Theor. Chim. Acta
68
, 445
(1985
).45.
W.
Kutzelnigg
and W.
Klopper
, J. Chem. Phys.
94
, 1985
(1991
).46.
W.
Klopper
and W.
Kutzelnigg
, Chem. Phys. Lett.
134
, 17
(1987
).47.
W.
Klopper
and C. C. M. J.
Samson
, J. Chem. Phys.
116
, 6397
(2002
).48.
F. R.
Manby
, J. Chem. Phys.
119
, 4607
(2003
).49.
S.
Ten-no
and F. R.
Manby
, J. Chem. Phys.
119
, 5358
(2003
).50.
S. J.
Ten-no
, J. Chem. Phys.
121
, 117
(2004
).51.
E. F.
Valeev
, Chem. Phys. Lett.
395
, 190
(2004
).52.
E. F.
Valeev
and C. L.
Jansen
, J. Chem. Phys.
121
, 1214
(2004
).53.
T. B.
Adler
, G.
Knizia
, and H.-J.
Werner
, J. Chem. Phys.
127
, 221106
(2007
).54.
H.-J.
Werner
, T. B.
Adler
, and F. R.
Manby
, J. Chem. Phys.
126
, 164102
(2007
).55.
T. D.
Crawford
, C. D.
Sherrill
, E. F.
Valeev
, J. T.
Fermann
, R. A.
King
, M. L.
Leininger
, S. T.
Brown
, C. L.
Janssen
, E. T.
Seidl
, J. P.
Kenny
, and W. D. J.
Allen
, J. Comp. Chem.
28
, 1610
(2007
).56.
H.-J.
Werner
, P. J.
Knowles
, F. R.
Manby
, M.
Schütz
et al., MOLPRO, version 2010.1, a package of ab initio programs, 20112010, see http://www.molpro.net.57.
J.
Zheng
, S. L.
Mielke
, K. L.
Clarkson
, and D. G.
Truhlar
, MSTor computer program, version 2011–2 (University of Minnesota, Minneapolis, 2011
).58.
J.
Zheng
, S. L.
Mielke
, K. L.
Clarkson
, and D. G.
Truhlar
, Comput. Phys. Commun.
183
, 1803
(2012
).59.
G. P.
Moss
, Pure Appl. Chem.
68
, 2193
(1996
).60.
See supplementary material at http://dx.doi.org/10.1063/1.4742968 for all the structures and corresponding zero-point-exclusive and zero-point- inclusive relative conformational energies for 1-butanol obtained with M08-SO and M06-2X density functionals and MG3S basis set.
© 2012 American Institute of Physics.
2012
American Institute of Physics
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