Supporting Information
Gas-Phase Ammonia Activation by Th, Th+ and Th2+: Reaction
Mechanisms, Bonding Analysis and Rate Constants Calculations
Wenxia Niu,[a] Hong Zhang,*[a] Peng Li,[b] and Tao Gao*[b]
Table of Contents
1. The relative energies of lowest stationary points on the potential energy
pathway.
Table S1. Relative energies (kcal/mol) of the stationary points on the reaction of Th + NH3
potential energy surface.
Table S2. Relative energies (kcal/mol) of the stationary points on the reaction of Th+ + NH3
potential energy surface.
Table S3. Relative energies (kcal/mol) of the stationary points on the reaction of Th2+ + NH3
potential energy surface.
2. The ELF localization domains corresponding to the lowest-energy minima and
transition states of Th+(2+) + NH3 reaction.
Fig. S1 ELF localization domains (η=0.70) of the lowest energy minima and transition states
corresponding to the Th+ + NH3 reaction pathway.
Fig. S2 ELF localization domains (η=0.70) of the lowest energy minima and transition states
corresponding to the Th2+ + NH3 reaction pathway.
3. Topological properties of the charge density calculated at the (3,-1) bond
critical points for Th+(2+) + NH3 reaction.
Table S4. Topological properties of the charge density calculated at the (3,-1) bond critical
points for all species involved in the Th+ + NH3 reaction pathway at PW91/SDD level of theory.
Table S5. Topological properties of the charge density calculated at the (3,-1) bond critical
points for all species involved in the Th2+ + NH3 reaction pathway at PW91/SDD level of
[a] College of Physical Science and Technology, Sichuan University, Chengdu 610065, China
E-mail: [email protected]
[b] Institute of Atomic and Molecular Physics, Sichuan University, Chengdu, 610065, China,
E-mail: [email protected]
1
theory.
4. IRC energy and Wiberg bond order along the reaction coordinate of the Th+(2+)
+ NH3.
Fig. S3 IRC energy and Wiberg bond order along the reaction coordinate s calculated at the
B3LYP/SDD levels corresponding to the Th+ + NH3. Black solid curves are the energy and
coloured curves are Wiberg bond order.
Fig. S4 IRC energy and Wiberg bond order along the reaction coordinate s calculated at the
B3LYP/SDD levels corresponding to the Th2+ + NH3. Black solid curves are the energy and
coloured curves are Wiberg bond order.
5. Computed VTST rate constants and temperature plots of Th +(2+) + NH3
reaction.
Fig. S5 Computed VTST rate constants and temperature plots of Th+ + NH3 reaction obtained
using PW91/SDD energies and frequencies: k versus T (left) and log10k versus 1000/T (right).
Fig. S6 Computed VTST rate constants and temperature plots of Th2+ + NH3 reaction obtained
using PW91/SDD energies and frequencies: k versus T (left) and log10k versus 1000/T (right).
6. Ab Initio molecular dynamics simulation of the product H2ThNH.
Fig. S7 The RMSD at different temperatures for the product H2ThNH.
References
2
1. The relative energies of lowest stationary points on the potential energy
pathway.
The relative energies of lowest stationary points on the potential energy pathway have
been calculated at different levels of theory and are given in Table S1, S2 and S3 for
Th, Th+ and Th2+ + NH3 reaction, respectively. Our calculations cover hybrid DFT
method, pure GGA functionals, GGA with spin-orbit effect, and couple-cluster
calculations. This series of methods ought to provide a broad investigation of the
structures and energetics corresponding to the reaction of Th atom with NH3. As can
be seen that the spin–orbit ZORA method also give good consistent relative energies
compared with ZORA-SR. It is consistent with the experiments results of Andews and
collaborators. 1, 2 They found that spin-orbit corrections have little effect on the
computed geometries for actinide molecular systems. In order to check whether our
results calculated by a higher wavefunction based correlation method within the same
consistent results, we chose to use single-point CCSD(T)/SDD calculations on
CCD/SDD optimized geometries. For the single-point CCSD(T) calculation, the
energies are reasonable close to those from PW91/SDD level, especially for the
barrier of the TS3 of Th + NH3 reaction. As seen from Table S1, the TS3 is found
18.48 and 18.86 kcal/mol above the intermediate at PW91/SDD and CCSD(T)/SDD
levels of theory, respectively. This conclusion is consistent with the recent study, 18
which shows that the single-point CCSD(T) calculations give reaction energies that
are close to those from DFT, especially for dissociation reactions of actinide element
compounds. Therefore, B3LYP/SDD and PW91/SDD have been chosen for the
bonding analysis.
Table S1. Relative energies (kcal/mol) of the stationary points on the reaction of Th+NH3
potential energy surface.
I(3A1)
TS1(3A)
II(1A) TS2(1A)
III(1A)
TS3(1A) ThNH+H2
B3LYP [a]
PW91 [a]
ZORA-SR [b]
ZORA-SO [c]
CCD [a]
CCSD(T) [d]
B3LYP [e]
<S2> [f]
<S2> [g]
46.020
41.458
45.520
43.480
35.135
35.796
46.9
2.010
2.026
64.107
54.454
54.020
52.770
57.715
65.975
64.1
2.024
2.059
0.000
0.000
0.000
0.000
0.000
0.000
0.0
0.000
0.000
22.057
13.551
13.340
13.380
23.779
19.283
22.0
0.000
0.000
-15.832
-20.638
-21.530
-21.620
-13.326
-14.650
-16.0
0.000
0.000
26.266
18.487
21.660
19.010
22.682
18.865
—
0.000
0.000
1.618
1.068
5.200
3.110
6.496
3.842
9.8
[a] SDD for Th and 6-311++G(d,p) for H and N atoms. [b] Frozen core TZP for Th and TZ2P
for H and N atoms, PW91/ ZORA-SR. [c] Frozen core TZP for Th and TZ2P for H and N
atoms, singlet point PW91/ZORA-SO results. [d] singlet point CCSD(T) results on the
CCD/SDD optimized geometries. [e] Ref. 6 [f] Expectation value of S2 at the B3LYP/SDD
level of theory. [g] Expectation value of S2 at the PW91/SDD level of theory.
3
Table S2. Relative energies (kcal/mol) of the stationary points on the reaction of Th+ + NH3 potential
energy surface.
I(2A)
TS1(2A) II(2A) TS2(2A) III(2A) TS3(2A) ThNH++H2 ThNH2++H
B3LYP [a]
PW91 [a]
ZORA-SR [b]
ZORA-SO [c]
CCD [a]
CCSD(T) [d]
<S2> [e]
<S2> [f]
33.116
32.231
36.760
34.080
23.710
27.964
0.967
0.755
51.333
47.450
49.270
48.960
56.982
55.148
0.812
0.887
0.000
0.000
0.000
0.000
0.000
0.000
0.751
0.752
43.294
34.479
—
57.563
50.148
0.757
0.755
41.673
34.342
34.370
34.480
48.002
48.061
0.766
0.756
21.904
14.538
14.130
14.410
23.524
23.398
0.751
0.752
10.959
11.123
11.850
12.790
14.095
11.514
71.720
72.915
75.410
75.670
61.246
58.761
[a] SDD for Th and 6-311++G(d,p) for H and N atoms. [b] Frozen core TZP for Th and TZ2P for H and N
atoms, PW91/ ZORA-SR. [c] Frozen core TZP for Th and TZ2P for H and N atoms, singlet point
PW91/ZORA-SO results. [d] singlet point CCSD(T) results on the CCD/SDD optimized geometries. [e]
Expectation value of S2 at the B3LYP/SDD level of theory. [f] Expectation value of S2 at the PW91/SDD
level of theory.
Table S3. Relative energies (kcal/mol) of the stationary points on the reaction of Th2+ + NH3 potential
energy surface.
I(3A) TS1(1A) II(1A) TS2(1A) III(1A) TS3(1A) ThNH2++H2 ThNH22++H
B3LYP [a]
PW91 [a]
ZORA-SR [b]
ZORA-SO [c]
CCD [a]
CCSD(T) [d]
<S2> [e]
<S2> [f]
15.456
17.843
20.310
20.360
20.176
23.814
2.001
2.002
50.824
46.606
49.600
46.690
49.867
46.527
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
0.000
128.032
112.869
112.340
111.990
146.059
125.913
0.000
0.000
111.096
107.558
97.200
96.540
128.557
108.292
0.000
0.000
20.494
15.179
18.210
18.550
24.721
21.336
0.000
0.000
15.464
13.319
15.470
16.120
17.343
15.942
70.091
67.796
69.610
68.520
71.432
67.768
[a] SDD for Th and 6-311++G(d,p) for H and N atoms. [b] Frozen core TZP for Th and TZ2P for H and N
atoms, PW91/ ZORA-SR. [c] Frozen core TZP for Th and TZ2P for H and N atoms, singlet point
PW91/ZORA-SO results. [d] singlet point CCSD(T) results on the CCD/SDD optimized geometries. [e]
Expectation value of S2 at the B3LYP/SDD level of theory. [f] Expectation value of S2 at the PW91/SDD
level of theory.
4
2. The ELF localization domains corresponding to the lowest-energy minima and
transition states of Th+(2+) + NH3 reaction.
Fig. S1 ELF localization domains (η=0.70) of the lowest energy minima and transition states
corresponding to the Th+ + NH3 reaction pathway.
Fig. S2 ELF localization domains (η=0.70) of the lowest energy minima and transition states
corresponding to the Th2+ + NH3 reaction pathway.
5
3. Topological properties of the charge density calculated at the (3,-1) bond
critical points for Th+(2+) + NH3 reaction.
Table S4. Topological properties of the charge density calculated at the (3,-1) bond
critical points for all species involved in the Th+ + NH3 reaction pathway at
PW91/SDD level of theory. [a]
species
ρ(r)
G(r)
V(r)
H(r)
∇2ρ(r)
I(2A)
TS1(2A)
II(2A)
TS2(2A)
III(2A)
TS3(2A)
Th―N
N―H1
N―H2
N―H3
Th―N
N―H1
N―H2
N―H3
Th―N
Th―H1
N―H2
N―H3
Th―N
Th―H1
N―H2
N―H3
Th―N
Th―H1
Th―H2
N―H3
Th―N
Th―H1
N―H2
N―H3
H1―H2
0.065
0.319
0.319
0.319
0.114
0.158
0.316
0.316
0.143
0.107
0.315
0.312
0.173
0.090
0.129
0.322
0.188
0.082
0.082
0.315
0.178
0.075
0.140
0.317
0.126
0.123
-1.458
-1.458
-1.458
0.173
-0.188
-1.457
-1.457
0.207
-0.049
-1.398
-1.353
0.296
-0.005
-0.059
-1.437
0.389
-0.001
-0.001
-1.469
0.343
0.071
-0.100
-1.495
-0.212
0.043
0.056
0.056
0.056
0.087
0.056
0.049
0.049
0.123
0.037
0.054
0.055
0.176
0.034
0.056
0.049
0.218
0.031
0.031
0.049
0.194
0.039
0.059
0.048
0.028
-0.054
-0.466
-0.466
-0.466
-0.130
-0.159
-0.464
-0.464
-0.194
-0.088
-0.457
-0.448
-0.278
-0.069
-0.126
-0.486
-0.339
-0.061
-0.061
-0.464
-0.301
-0.061
-0.144
-0.472
-0.110
-0.011
-0.410
-0.410
-0.410
-0.043
-0.103
-0.415
-0.415
-0.071
-0.051
-0.403
-0.393
-0.102
-0.035
-0.070
-0.437
-0.121
-0.030
-0.030
-0.415
-0.107
-0.022
-0.085
-0.424
-0.082
[a] ρ(bcp) and ∇2ρ(bcp) in au. For NH3, N-H ρ(bcp) = 0.328; ∇2ρ(bcp)= -1.398;
H(r)= -0.410.
6
Table S5. Topological properties of the charge density calculated at the (3,-1) bond
critical points for all species involved in the Th2+ + NH3 reaction pathway at
PW91/SDD level of theory. [a]
species
ρ(r)
G(r)
V(r)
H(r)
∇2ρ(r)
I(3A)
TS1(1A)
II(1A)
TS2(1A)
III(1A)
TS3(1A)
Th―N
N―H1
N―H2
N―H3
Th―N
N―H1
N―H2
N―H3
Th―N
Th―H1
N―H2
N―H3
Th―N
Th―H1
Th―H2
N―H3
Th―N
Th―H1
Th―H2
N―H3
Th―N
Th―H1
N―H2
N―H3
H1―H2
0.066
0.314
0.314
0.314
0.136
0.148
0.306
0.306
0.162
0.122
0.301
0.306
0.220
0.085
0.091
0.295
0.192
0.093
0.093
0.305
0.195
0.088
0.151
0.307
0.113
0.114
-1.459
-1.459
-1.459
0.161
-0.160
-1.468
-1.468
0.205
-0.112
-1.364
-1.427
0.220
-0.039
-0.049
-1.424
0.402
-0.057
-0.057
-1.563
0.350
0.029
-0.149
-1.557
-0.151
0.041
0.047
0.047
0.047
0.103
0.053
0.044
0.044
0.143
0.036
0.048
0.046
0.217
0.025
0.028
0.042
0.225
0.026
0.026
0.037
0.217
0.039
0.059
0.039
0.028
-0.054
-0.459
-0.459
-0.459
-0.166
-0.146
-0.455
-0.455
-0.236
-0.100
-0.436
-0.448
-0.379
-0.059
-0.068
-0.439
-0.351
-0.067
-0.067
-0.465
-0.347
-0.071
-0.155
-0.469
-0.095
-0.013
-0.412
-0.412
-0.412
-0.063
-0.93
-0.411
-0.411
-0.093
-0.064
-0.388
-0.402
-0.162
-0.034
-0.040
-0.397
-0.126
-0.041
-0.041
-0.428
-0.130
-0.032
-0.096
-0.430
-0.067
[a] ρ(bcp) and ∇2ρ(bcp) in au. For NH3, N-H ρ(bcp) = 0.328; ∇2ρ(bcp)= -1.398;
H(r)= -0.410.
7
4. IRC energy and Wiberg bond order along the reaction coordinate of the Th+(2+)
+ NH3.
Fig. S3 IRC energy and Wiberg bond order along the reaction coordinate s calculated at the
B3LYP/SDD levels corresponding to the Th+ + NH3. Black solid curves are the energy and
coloured curves are wiberg bond order. (a) Th+-NH3→TS1→HThNH2+; (b)
HThNH2+→TS2→HNThH2+; (c) HThNH2+→TS3→H2-ThNH+.
8
Fig. S4 IRC energy and Wiberg bond order along the reaction coordinate s calculated at the
B3LYP/SDD levels corresponding to the Th2+ + NH3. Black solid curves are the energy and
coloured
curves
are
wiberg
bond
order.
(a)
Th2+-NH3→TS1→HThNH22+;
HThNH22+→TS2→HNThH22+; (c) HThNH22+→TS3→H2-ThNH2+.
9
(b)
5. Computed VTST rate constants and temperature plots of Th +(2+) + NH3
reaction.
Fig. S5 Computed VTST rate constants and temperature plots of Th+ + NH3 reaction obtained
using PW91/SDD energies and frequencies: k versus T (left) and log10k versus 1000/T (right).
10
Fig. S6 Computed VTST rate constants and temperature plots of Th2+ + NH3 reaction obtained
using PW91/SDD energies and frequencies: k versus T (left) and log10k versus 1000/T (right).
6. Ab Initio molecular dynamics simulation of the product H2ThNH.
Ab Initio molecular dynamics simulation was performed, with the aim of confirm the
thermal stability of the product H2ThNH. Simulations are carried out for almost 6 ps
using the BOMD method 3 in Gaussian03. Our dynamics simulation result indicates
that the H2ThNH is stabilized. We plotted the root mean square displacement (RMSD)
through time at different temperature (300 and 500K) using the dynamics simulations
results. The results are shown in the following figures. These figures indicate that the
H2ThNH structure keeps its identity at both room temperature (300 K) and high
temperature (450 K).
11
Fig. S7 The RMSD at different temperatures for the product H2ThNH.
References
[1] J. T. Lyon, L. Andews, P. Malmqvist, B.O. Roos, T. Yang, B. E. Bursten, Inorg. Chem. 2007,
46, 4917.
[2] L. Gagliardi, B. O. Roos, PÅ. Malmqvist, J. M. Dyke, J. Phys. Chem. A 2001, 105, 10602.
[3] V. Bakken, J. M. Millam and H. B. Schlegel, J. Chem. Phys., 1999, 111, 8773.
12