The CH3 + HO2 reaction system was studied theoretically by a newly developed, HEAT345-(Q) method based CHEAT1 protocol and includes the combined singlet and triplet potential energy surfaces. The main simplification is based on the CCSDT(Q)/cc-pVDZ calculation which is computationally inexpensive. Despite the economic and black-box treatment of higher excitations, the results are within 0.6 kcal/mol of the highly accurate literature values. Furthermore, the CHEAT1 surpassed the popular standard composite methods such as CBS-4M, CBS-QB3, CBS-APNO, G2, G3, G3MP2B3, G4, W1U, and W1BD mainly due to their poor performance in characterizing transition states (TS). For TS structures, various standard DFT and MP2 method have also been tested against the resulting CCSD/cc-pVTZ geometry of our protocol. A fairly good agreement was only found in the cases of the B2PLYP and BHandHLYP functionals, which were able to reproduce the structures of all TS studied within a maximum absolute deviation of 7%. The complex reaction mechanism was extended by three new low lying reaction channels. These are indirect water elimination from CH3OOH resulted formaldehyde, H2 elimination yielded methylene peroxide, and methanol and reactive triplet oxygen were formed via H-shift in the third channel. CHEAT1 protocol based on HEAT345-(Q) method is a robust, general, and cheap alternative for high accurate kinetic calculations.
REFERENCES
1.
J. J.
Scire
, F. L.
Dryer
, and R. A.
Yetter
, Int. J. Chem. Kinet.
33
(12
), 784
-802
(2001
). 2.
J. J.
Scire
, R. A.
Yetter
, and F. L.
Dryer
, Int. J. Chem. Kinet.
33
(2
), 75
-100
(2001
). 3.
D. L.
Baulch
, C. T.
Bowman
, C. J.
Cobos
, R. A.
Cox
, T.
Just
, J. A.
Kerr
, M. J.
Pilling
, D.
Stocker
, J.
Troe
, W.
Tsang
, R. W.
Walker
, and J.
Warnatz
, J. Phys. Chem. Ref. Data
34
(3
), 757
-1397
(2005
). 4.
Z. K.
Hong
, D. F.
Davidson
, K. Y.
Lam
, and R. K.
Hanson
, Combust. Flame
159
(10
), 3007
-3013
(2012
). 5.
M.
Sangwan
and L. N.
Krasnoperov
, J. Phys. Chem. A
117
(14
), 2916
-2923
(2013
). 6.
A. W.
Jasper
, S. J.
Klippenstein
, and L. B.
Harding
, Proc. Combust. Inst.
32
, 279
-286
(2009
). 7.
R. S.
Zhu
and M. C.
Lin
, J. Phys. Chem. A
105
(25
), 6243
-6248
(2001
). 8.
A.
Tajti
, P. G.
Szalay
, A. G.
Csaszar
, M.
Kallay
, J.
Gauss
, E. F.
Valeev
, B. A.
Flowers
, J.
Vazquez
, and J. F.
Stanton
, J. Chem. Phys.
121
(23
), 11599
-11613
(2004
). 9.
K. A.
Peterson
, D.
Feller
, and D. A.
Dixon
, Theor. Chem. Acc.
131
(1
), 1079
(2012
). 10.
T. L.
Nguyen
, J.
Li
, R.
Dawes
, J. F.
Stanton
, and H.
Guo
, J. Phys. Chem. A
117
(36
), 8864
-8872
(2013
). 11.
D.
Feller
, J. Chem. Phys.
96
(8
), 6104
-6114
(1992
). 12.
T.
Helgaker
, W.
Klopper
, H.
Koch
, and J.
Noga
, J. Chem. Phys.
106
(23
), 9639
-9646
(1997
). 13.
R. L.
Martin
, J. Phys. Chem.
87
(5
), 750
-754
(1983
). 14.
G. D.
Purvis
and R. J.
Bartlett
, J. Chem. Phys.
76
(4
), 1910
-1918
(1982
). 15.
G. E.
Scuseria
, C. L.
Janssen
, and H. F.
Schaefer
, J. Chem. Phys.
89
(12
), 7382
-7387
(1988
). 16.
T. H.
Dunning
, J. Chem. Phys.
90
(2
), 1007
-1023
(1989
). 17.
M. J.
Frisch
, G. W.
Trucks
, H. B.
Schlegel
, G. E.
Scuseria
, M. A.
Robb
, J. R.
Cheeseman
, G.
Scalmani
, V.
Barone
, B.
Mennucci
, G. A.
Petersson
, H.
Nakatsuji
, M.
Caricato
, X.
Li
, H. P.
Hratchian
, A. F.
Izmaylov
, J.
Bloino
, G.
Zheng
, J. L.
Sonnenberg
, M.
Hada
, M.
Ehara
, K.
Toyota
, R.
Fukuda
, J.
Hasegawa
, M.
Ishida
, T.
Nakajima
, Y.
Honda
, O.
Kitao
, H.
Nakai
, T.
Vreven
, J. A.
Montgomery
, Jr., J. E.
Peralta
, F.
Ogliaro
, M.
Bearpark
, J. J.
Heyd
, E.
Brothers
, K. N.
Kudin
, V. N.
Staroverov
, R.
Kobayashi
, J.
Normand
, K.
Raghavachari
, A.
Rendell
, J. C.
Burant
, S. S.
Iyengar
, J.
Tomasi
, M.
Cossi
, N.
Rega
, J. M.
Millam
, M.
Klene
, J. E.
Knox
, J. B.
Cross
, V.
Bakken
, C.
Adamo
, J.
Jaramillo
, R.
Gomperts
, R. E.
Stratmann
, O.
Yazyev
, A. J.
Austin
, R.
Cammi
, C.
Pomelli
, J. W.
Ochterski
, R. L.
Martin
, K.
Morokuma
, V. G.
Zakrzewski
, G. A.
Voth
, P.
Salvador
, J. J.
Dannenberg
, S.
Dapprich
, A. D.
Daniels
, Ö
Farkas
, J. B.
Foresman
, J. V.
Ortiz
, J.
Cioslowski
, and D. J.
Fox
, Gaussian’09, Gaussian, Inc., Wallingford CT, 2009.18.
NIST Computational Chemistry Comparison and Benchmark Database, NIST Standard Reference Database Number 101, Release 16a, August 2013,
edited by R. D. Johnson III, http://cccbdb.nist.gov.19.
See supplementary material at http://dx.doi.org/10.1063/1.4907014 for harmonic vibrational frequencies and rotational constant, total and relative energies from CHEAT1 calculation and T1, S2, VEE values of the species.
20.
R.
Izsak
, M.
Szori
, P. J.
Knowles
, and B.
Viskolcz
, J. Chem. Theory Comput.
5
(9
), 2313
-2321
(2009
). 21.
D. E.
Woon
and T. H.
Dunning
, J. Chem. Phys.
98
(2
), 1358
-1371
(1993
). 22.
J. D.
Watts
, J.
Gauss
, and R. J.
Bartlett
, J. Chem. Phys.
98
(11
), 8718
-8733
(1993
). 23.
R. A.
Kendall
, T. H.
Dunning
, and R. J.
Harrison
, J. Chem. Phys.
96
(9
), 6796
-6806
(1992
). 24.
H.
Koch
and P.
Jorgensen
, J. Chem. Phys.
93
(5
), 3333
-3344
(1990
). 25.
H.
Koch
, R.
Kobayashi
, A. S.
Demeras
, and P.
Jorgensen
, J. Chem. Phys.
100
(6
), 4393
-4400
(1994
). 26.
J. F.
Stanton
and R. J.
Bartlett
, J. Chem. Phys.
98
(9
), 7029
-7039
(1993
). 27.
28.
T.
Schwabe
and S.
Grimme
, Phys. Chem. Chem. Phys.
9
(26
), 3397
-3406
(2007
). 29.
S.
Grimme
, J. Comput. Chem.
27
(15
), 1787
-1799
(2006
). 30.
A. D.
Becke
, J. Chem. Phys.
98
(2
), 1372
-1372
(1993
). 31.
C.
Lee
, W.
Yang
, and R. G.
Parr
, Phys. Rev. B: Condens. Matter
37
(2
), 785
-789
(1988
). 32.
S. H.
Vosko
, L.
Wilk
, and M.
Nusair
, Can. J. Phys.
58
(8
), 1200
-1211
(1980
). 33.
P. J.
Stephens
, F. J.
Devlin
, C. F.
Chabalowski
, and M. J.
Frisch
, J. Phys. Chem.
98
(45
), 11623
-11627
(1994
). 34.
A. D.
Boese
and J. M. L.
Martin
, J. Chem. Phys.
121
(8
), 3405
-3416
(2004
). 35.
T.
Yanai
, D. P.
Tew
, and N. C.
Handy
, Chem. Phys. Lett.
393
(1-3
), 51
-57
(2004
). 36.
Y.
Zhao
and D. G.
Truhlar
, Theor. Chem. Acc.
120
(1-3
), 215
-241
(2008
). 37.
Y.
Zhao
and D. G.
Truhlar
, J. Phys. Chem. A
110
(15
), 5121
-5129
(2006
). 38.
Y.
Zhao
and D. G.
Truhlar
, J. Phys. Chem. A
110
(49
), 13126
-13130
(2006
). 39.
C.
Adamo
and V.
Barone
, J. Chem. Phys.
108
(2
), 664
-675
(1998
). 40.
A. D.
Boese
and N. C.
Handy
, J. Chem. Phys.
116
(22
), 9559
-9569
(2002
). 41.
J. M.
Tao
, J. P.
Perdew
, V. N.
Staroverov
, and G. E.
Scuseria
, Phys. Rev. Lett.
91
(14
), 146401
(2003
). 42.
J. W.
Ochterski
, G. A.
Petersson
, and J. A.
Montgomery
, J. Chem. Phys.
104
(7
), 2598
-2619
(1996
). 43.
J. A.
Montgomery
, M. J.
Frisch
, J. W.
Ochterski
, and G. A.
Petersson
, J. Chem. Phys.
112
(15
), 6532
-6542
(2000
). 44.
J. A.
Montgomery
, M. J.
Frisch
, J. W.
Ochterski
, and G. A.
Petersson
, J. Chem. Phys.
110
(6
), 2822
-2827
(1999
). 45.
L. A.
Curtiss
, K.
Raghavachari
, G. W.
Trucks
, and J. A.
Pople
, J. Chem. Phys.
94
(11
), 7221
-7230
(1991
). 46.
L. A.
Curtiss
, K.
Raghavachari
, P. C.
Redfern
, V.
Rassolov
, and J. A.
Pople
, J. Chem. Phys.
109
(18
), 7764
-7776
(1998
). 47.
L. A.
Curtiss
, P. C.
Redfern
, K.
Raghavachari
, V.
Rassolov
, and J. A.
Pople
, J. Chem. Phys.
110
(10
), 4703
-4709
(1999
). 48.
A. G.
Baboul
, L. A.
Curtiss
, P. C.
Redfern
, and K.
Raghavachari
, J. Chem. Phys.
110
(16
), 7650
-7657
(1999
). 49.
L. A.
Curtiss
, P. C.
Redfern
, and K.
Raghavachari
, J. Chem. Phys.
126
(8
), 084108
(2007
). 50.
E. C.
Barnes
, G. A.
Petersson
, J. A.
Montgomery
, M. J.
Frisch
, and J. M. L.
Martin
, J. Chem. Theory Comput.
5
(10
), 2687
-2693
(2009
). 51.
H.-J.
Werner
, P. J.
Knowles
, G.
Knizia
, F. R.
Manby
, M.
Schütz
, P.
Celani
, T.
Korona
, R.
Lindh
, A.
Mitrushenkov
, G.
Rauhut
, K. R.
Shamasundar
, T. B.
Adler
, R. D.
Amos
, A.
Bernhardsson
, A.
Berning
, D. L.
Cooper
, M. J. O.
Deegan
, A. J.
Dobbyn
, F.
Eckert
, E.
Goll
, C.
Hampel
, A.
Hesselmann
, G.
Hetzer
, T.
Hrenar
, G.
Jansen
, C.
Köppl
, Y.
Liu
, A. W.
Lloyd
, R. A.
Mata
, A. J.
May
, S. J.
McNicholas
, W.
Meyer
, M. E.
Mura
, A.
Nicklass
, D. P.
O’Neill
, P.
Palmieri
, D.
Peng
, K.
Pflüger
, R.
Pitzer
, M.
Reiher
, T.
Shiozaki
, H.
Stoll
, A. J.
Stone
, R.
Tarroni
, T.
Thorsteinsson
, and M.
Wang
, molpro, version 2010.1, a package of ab initio programs, 2010, see http://www.molpro.net.52.
H. J.
Werner
, P. J.
Knowles
, G.
Knizia
, F. R.
Manby
, and M.
Schutz
, Wiley Interdiscip. Rev.: Comput. Mol. Sci.
2
(2
), 242
-253
(2012
). 53.
B.
Ruscic
, R. E.
Pinzon
, G.
von Laszewski
, D.
Kodeboyina
, A.
Burcat
, D.
Leahy
, D.
Montoya
, and A. F.
Wagner
, J. Phys.: Conf. Ser.
16
, 561–570 (2005). 54.
E.
Goos
, A.
Burcat
, and B.
Ruscic
, Extended Third Millennium Ideal Gas and Condensed Phase Thermochemical Database for Combustion with Updates from Active Thermochemical Tables, Update of “Third Millennium Ideal Gas and Condensed Phase Thermochemical Database for Combustion with Updates from Active Thermochemical Tables,” 2005.55.
B.
Ruscic
, R. E.
Pinzon
, M. L.
Morton
, N. K.
Srinivasan
, M. C.
Su
, J. W.
Sutherland
, and J. V.
Michael
, J. Phys. Chem. A
110
(21
), 6592
-6601
(2006
). 56.
R. E.
Pinzon
, B.
Ruscic
, M. L.
Morton
, G.
von Laszevski
, S. J.
Bittner
, S. G.
Nijsure
, K. A.
Amin
, M.
Minkoff
, and A. F.
Wagner
, J. Phys. Chem. A
108
(45
), 9979
-9997
(2004
). 57.
N. K.
Srinivasan
, J. V.
Michael
, L. B.
Harding
, and S. J.
Klippenstein
, Combust. Flame
149
(1-2
), 104
-111
(2007
). 58.
D.
Schroder
, C. A.
Schalley
, N.
Goldberg
, J.
Hrusak
, and H.
Schwarz
, Chem. - Eur. J.
2
(10
), 1235
-1242
(1996
). 59.
J.
Matthews
, A.
Sinha
, and J. S.
Francisco
, J. Chem. Phys.
122
(22
), 221101
(2005
). 60.
M. T.
Nguyen
, T. L.
Nguyen
, V. T.
Ngan
, and H. M. T.
Nguyen
, Chem. Phys. Lett.
448
(4-6
), 183
-188
(2007
). 61.
M.
Szori
, C.
Fittschen
, I. G.
Csizmadia
, and B.
Viskolcz
, J. Chem. Theory Comput.
2
(6
), 1575
-1586
(2006
). 62.
M.
Szori
, I. G.
Csizmadia
, and B.
Viskolcz
, J. Chem. Theory Comput.
4
(9
), 1472
-1479
(2008
). 63.
T. J.
Lee
, A. P.
Rendell
, and P. R.
Taylor
, J. Phys. Chem.
94
(14
), 5463
-5468
(1990
). 64.
M.
Szori
, T.
Abou-Abdo
, C.
Fittschen
, I. G.
Csizmadia
, and B.
Viskolcz
, Phys. Chem. Chem. Phys.
9
(16
), 1931
-1940
(2007
). © 2015 AIP Publishing LLC.
2015
AIP Publishing LLC
You do not currently have access to this content.
