Supplementary Material
Reaction dynamics of O(1D) + HCOOD/DCOOH investigated with
time-resolved Fourier-transform infrared emission spectroscopy
Shang-Chen Huang,1 N. T. Nghia,2 Raghunath Putikam,1 Hue M. T. Nguyen,3 M. C. Lin,1, * Soji
Tsuchiya,1, †, * and Yuan-Pern Lee1, 4, *
1Department
of Applied Chemistry and Institute of Molecular Science, National Chiao Tung
University, Hsinchu 30010, Taiwan.
2 School of Chemical Engineering - Hanoi University of Science and Technology, Hanoi,
Vietnam
3Center for Computational Science and Faculty of Chemistry, Hanoi National University of
Education, Hanoi, Vietnam
4Institute of Atomic and Molecular Sciences, Academia Sinica, Taipei 10617, Taiwan
(Received: August xx, 2014; Accepted xxxx xx, 2014)
Running title: Dynamics of O(1D) + HCOOD/DCOOH
Key words: chemical dynamics, O(1D), HCOOH, time-resolved IR spectroscopy,
HCOOD, DCOOH
†
Present address: Research Institute of Science and Engineering, Waseda University,
Ookubo, Shinjuku-ku, Tokyo 169-8555, Japan
 To whom correspondence should be addressed. E-mail: chemmcl@emory.edu
(M.C.L.); tsuchis@sepia.plala.or.jp (S.T.); yplee@mail.nctu.edu.tw (Y.-P.L.).
Comparison of rate coefficients (in cm3 molecule1 s1) predicted for important
reactions of O(1D) + HCOOH with and without Eckart tunneling corrections
according to potential-energy surfaces predicted with the
CCSD(T)/6-311++G(3df,2p)// B3LYP/6-311++G(3df,2p) method is presented in
Table SI.
Plot of rotational temperature TR of OH (v = 13) from O(1D) + DCOOH as a
function of time is shown in Fig. S1. Potential-energy scheme of the insertion reaction
of O(1D) + HCOOH computed with the CCSD(T)/6-311++G(3df,2p)
//B3LYP/6-311++G(3df,2p)+ZPVE method is shown in Fig. S2. The optimized
geometries of some important transition states computed at the
B3LYP/6-311++g(3df,2p) or CAS(8,8)/6-311++g(3df,2p) level is shown in Fig. S3.
Predicted rate coefficients k8k10 of the unimolecular decomposition channels of
HOC(O)OD (IS8) in the O(1D) + HCOOD reaction as a function of energy is shown
in Fig. S4. Predicted rate coefficients k11 and k12 of the unimolecular decomposition
channels of HC(O)OOD (IS2) in the O(1D) + HCOOD reaction as a function of
energy is shown in Fig. S5. Predicted rate coefficients k13k15 of the unimolecular
decomposition channels of DOC(O)OH (IS8) in the O(1D) + DCOOH reaction as a
function of energy is shown in Fig. S6. Predicted rate coefficients k16 and k17 of the
unimolecular decomposition channels of DC(O)OOH (IS2) in the O(1D) + DCOOH
reaction as a function of energy is shown in Fig. S7.
Table S1: Rate coefficients (in cm3 molecule1 s1) predicted for important reactions
of O(1D) + HCOOH with and without Eckart tunneling corrections according to
potential-energy surfaces predicted with the CCSD(T)/6-311++G(3df,2p)//
B3LYP/6-311++G(3df,2p) method.
reaction
T = 350 Ka
products
(with tunneling) (without tunneling)
k1 IS8* → CO2 + H2O
5.321011
5.331011
k2 IS8* → OH + HOCO
4.301011
4.291011
k3 IS8* → CO3 + H2
2.921016
2.901016
k4 IS2* → OH + HC(O)O
7.301011
7.301011
k5 IS2* → CO2 + H2O
7.861015
7.901015
a
Rate coefficients are independent of pressure for P  20 atm.
FIG. S1. Plot of rotational temperature TR of OH (v = 13) from O(1D) + DCOOH as
a function of time. The data extrapolated to t = 0 are indicated with filled symbols.
151.5
E (kJ/mol)
39.3
T1P3
17.2
0.0
79.9
RA-cis
0.0
21.3
15.9
T1P1
T1/7
14.6
RA
(HCOOH+O)
10.0
T7P1
T6P2
HCO+HOO
-24.3
PR9 -83.7
T1P8
T9/1
-75.7 -80.8
T1/2 T9/3
-137.7
IS1
-145.2
T9/7 (HC(O)O(O)H)
-169.5
T9/6
-23.0
-28.5
-28.9
T2/3
T2P4
-76.6
T2P5
T4/7
-94.6
-50.0
55.2
-166.9
T2/5
IS2
(HC(O)OOH)
-157.3
-126.8
-160.2
-119.7 -120.9
T2P6 T8P4
IS7
IS4
-175.3
(cis-HOC(H)OO) (trans-HOC(H)OO)
T3P8
-215.9
IS9
(OOC(H)OH)
-341.0
CO+H2O-O
-70.3
T3/4
T6/7
T3/8
-217.1 -221.3
IS3
-277.0
T5/6
(HOCOOH)-228.4
-297.1
IS6
T5/8 (trans-HOC(O2)H)
IS5
(cis-HOC(O2)H)
-100.0
COH+HOO
PR10
TP8P7
-126.8
PR3
-118.4
TP8P11
-127.2
PR2
-166.9
H2O+cyc_COO-168.2
TP7P11
-190.0 PR7 HC(O)O+OH
CH2O+O2
-227.6 PR1
HOCO+OH
-231.0
PR8
-243.5
PR11
CO3+H2
PR4
CO2+H+OH
-325.1
CO+H2O2
PR5
-500.4
T8P6
-641.0
-150.0
-674.5
T8ct
IS8
cis-trans-HOC(O)OH)
-680.7
IS8
cis-cis-HOC(O)OH)
-711.7
PR6
CO2+H2O
FIG. S2. Potential-energy scheme of the insertion reaction of O(1D) + HCOOH computed with the CCSD(T)/6-311++G(3df,2p)//B3LYP/6-311++G(3df,2p)
+ ZPVE method. Energy is in kJ mol1.
FIG. S3. The optimized geometries of some important transition states computed at the
B3LYP/6-311++g(3df,2p) level. Com1 and Com2 are optimized at the CAS(8,8)/6-311++g(3df,2p) level.
(Length in Å and angle in degree).
FIG. S4. Predicted rate coefficients k8k10 of the unimolecular decomposition channels of HOC(O)OD
(IS8) in the O(1D) + HCOOD reaction as a function of energy.
FIG. S5. Predicted rate coefficients k11 and k12 of the unimolecular decomposition channels of
HC(O)OOD (IS2) in the O(1D) + HCOOD reaction as a function of energy.
FIG. S6. Predicted rate coefficients k13k15 of the unimolecular decomposition channels of DOC(O)OH
(IS8) in the O(1D) + DCOOH reaction as a function of energy.
FIG. S7. Predicted rate coefficients k16 and k17 of the unimolecular decomposition channels of
DC(O)OOH (IS2) in the O(1D) + DCOOH reaction as a function of energy.