The Stable of Noble Gas

連結點 HCCArF  C2H3ArF  OBOArH   OBNBArF  HNBArF  CH3NBArF

apdz和apcdz之basis set差異 、 OBArF與其TS之結構比較、 總整理

HCCArF 2006/06/02

單位：Å
R ( F-Ng )
R ( Ng-C )
R ( C-C )
R ( C-H )
Ng = Ar        
MP2/6-31+G**
1.929
1.850
1.226
1.065
MP2/aug-cc-pVDZ
1.919
1.868
1.235
1.076
MP2(FULL)/aug-cc-pVDZ
1.918
1.862
1.234
1.075
MP2/aug-cc-pCVDZ
1.916
1.856
1.233
1.075
MP2(FULL)/aug-cc-pCVDZ
1.916
1.850
1.232
1.074
MP2/aug-cc-pVTZ
1.894
1.799
1.215
1.063
CCSD(T)/6-311++G(2d,2p)
1.948
1.898
1.211
1.065
CCSD(T)/aug-cc-pVDZ
1.972
1.952
1.232
1.079
Ng = Kr
MP2/6-31+G**
1.997
1.949
1.223
1.065
MP2/aug-cc-pVDZ
1.988
1.939
1.235
1.075
MP2/aug-cc-pVTZ
1.967
1.908
1.216
1.063

 

單位：kcal/mol
rel. to HCC+Ar+F
rel. to HCCF+Ar
rel. to HF+Ar+C2
linear barrier
bending barrier
Ng = Ar          
MP2/6-31+G**
-14.6
126.2
28.0
18.8
36.3
MP2/aug-cc-pVDZ
-15.2
127.3
25.8
23.1
33.8
MP2(full)/aug-cc-pVDZ
-16.3 (-4.9)
126.9 (126.8)
24.5
23.7
33.6 (33.7)
MP2/aug-cc-pCVDZ
-16.0
126.7
25.3
23.8
33.9
MP2(full)/aug-cc-pCVDZ
-17.0
126.4
24.3
24.2
33.6
CCSD(T)/aug-cc-pVDZ//MP2(full)/aug-cc-pVDZ
3.3
127.7
30.1
34.7
CCSD(T)/aug-cc-pCVDZ//MP2/aug-cc-pCVDZ
2.5
127.2
29.2
23.4
34.8
CCSD(T,full)/aug-cc-pCVDZ//MP2(full)/aug-cc-pCVDZ
1.6
126.9
27.9
34.5
MP2/aug-cc-pVTZ
-24.4
124.8
15.8
CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVTZ
-5.0
126.9
19.8
14.4
33.8
CCSD(T)/6-311++G(2d,2p)
3.2
CCSD(T)/aug-cc-pVDZ
4.8
127.2
29.6
 
UMPW1PW91/aug-cc-pVDZ
-3.5
  
   
UMPW1PW91/aug-cc-pVTZ
-7.1
  
   
Ng = Kr
MP2/6-31+G**
-48.4
92.4
-5.8
31.5
52.0
MP2/aug-cc-pVDZ
-45.8
96.7
-4.8
32.3
44.4
MP2/aug-cc-pVTZ
-54.4
94.8
-14.2
39.9
42.8
CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVTZ
-34.4
97.3
-9.6
42.9

C2H3ArF 2006/06/02

單位：Å
R ( F-Ar )
R ( Ar-C )
R ( C-C )
R ( C-H )
Ng = Ar
MP2/6-31+G**
2.053
1.848
1.323
1.081
MP2/aug-cc-pVDZ
2.039
1.871
1.333
1.094
MP2/aug-cc-pVTZ
2.001
1.842
1.317
1.081

 

單位：kcal/mol
rel. to C2H3+Ar+F
rel. to C2H3F+Ar
linear barrier
bending barrier
Ng = Ar        
MP2/6-31+G**
-2.2
129.9
38.9
11.5
MP2/aug-cc-pVDZ
-6.5
126.6
39.6
12.1
MP2/aug-cc-pVTZ
-14.9
123.2
42.3
13.4

OBOArH2006/06/06

 

單位：Å
R ( H-Ar )
R ( Ar-O )
R ( O-B )
R ( B-O )
Ng = Ar
MP2/aug-cc-pVDZ
1.309
2.152
1.309
1.245
MP2/aug-cc-pVTZ
1.301
2.161
1.301
1.247

 

單位：kcal/mol
rel. to OBO +Ar+H
rel. to OBOH+Ar
linear barrier
bending barrier
Ng = Ar        
MP2/aug-cc-pVDZ
-0.6
127.8
21.1
12.6
MP2/aug-cc-pVTZ
-14.5
123.9
25.2
13.8
CCSD(T)/6-311++G(2d,2p)//MP2/aug-cc-pVDZ
8.2
128.1
11.1
14.1
CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ
9.0
127.6
9.3
13.1
CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVDZ
2.3
124.7
14.5
13.9
CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVTZ
1.8
124.7
14.2
13.9

OBNBArF2006/06/06

單位：Å
 R( O-B ) R ( B-N ) R ( N-B ) R ( B-Ng ) R ( Ng-F )
Ng = Ar
MP2/aug-cc-pVDZ
1.227
1.398
1.259
1.824
2.018
MP2/aug-cc-pVTZ
1.221
1.389
1.250
1.794
1.981
Ng = Kr
MP2/aug-cc-pVDZ
1.228
1.394
1.263
1.973
2.046
MP2/aug-cc-pVTZ
1.222
1.386
1.254
1.945
2.024

 

單位：kcal/mol
 S-T gap rel. to OBNB + Ng + F rel. to OBNBF + Ng Linear Barrier Bending Barrier
Ng = Ar    
MP2/aug-cc-pVDZ
138.0
-1.8
157.8
36.9
15.9
MP2/aug-cc-pVTZ
141.2
-11.3
158.8
40.3
16.6
CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ
127.9
5.5
156.9
16.9
CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVTZ
130.5
-2.6
159.6
17.1
Ng = Kr
MP2/aug-cc-pVDZ
153.6
-26.8
132.7
26.4
MP2/aug-cc-pVTZ
154.6
-25.1
144.9
25.7
CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ
142.0
-19.3
132.2
27.1
CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVTZ
145.3
-27.3
134.9
26.3

HNBArF2006/06/11

 

單位：Å
R ( H-N )
R ( N-B )
R ( B-Ng )
R ( Ng-F )
Ng = Ar
MP2/6-311+G*
0.999
1.235
1.776
2.120
MP2/aug-cc-pVDZ
1.003
1.244
1.804
2.065
MP2(full)/aug-cc-pVDZ
1.003
1.242
1.801
2.065
MP2/aug-cc-pVTZ
0.995
1.236
1.780
2.026
CCSD(T)/6-311+G*
1.000
1.225
1.810
2.125
CCSD(T)/aug-cc-pVTZ
0.995
1.234
1.799
2.033
Ng = Kr
MP2/6-311+G*
0.998
1.241
1.961
2.099
MP2/aug-cc-pVTZ
0.995
1.240
1.937
2.060
CCSD(T)/6-311+G*
0.999
1.240
1.985
2.108
Ng = Xe
MP2/6-311+G*
0.998
1.245
2.152
2.175
MP2/aug-cc-pVTZ
0.995
1.244
2.142
2.144
CCSD(T)/6-311+G*
0.999
1.244
2.175
2.176
CCSD(T)/aug-cc-pVTZ
0.994
1.242
2.159
2.142

 

單位：kcal/mol
 rel. to HNB + Ng + F rel. to HNBF + Ng Linear Barrier Bending Barrier
Ng = Ar    
MP2/6-311+G*
-1.7
158.1
39.3
11.6
MP2/aug-cc-pVDZ
-9.1
149.1
41.1
13.8
MP2(full)/aug-cc-pVDZ
-10.2
148.7
41.3
13.7
MP2/aug-cc-pVTZ
-18.2
150.0
45.1
14.5
CCSD(T)/6-311+G*
6.1
157.2
13.0
12.6
CCSD(T)/6-311++G(2d,2p)//MP2/aug-cc-pVDZ
-0.1
154.4
11.2
16.4
CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ
-0.2
148.7
10.6
14.6
CCSD(T,full)/aug-cc-pVDZ//MP2(full)/aug-cc-pVDZ
-1.3
148.3
10.8
14.6
CCSD(T)/aug-cc-pVTZ
-7.4
151.5
18.6
14.9
Ng = Kr
MP2/6-311+G*
-22.8
136.9
42.2
23.6
MP2/aug-cc-pVTZ
-41.0
127.1
45.7
23.3
CCSD(T)/6-311+G*
-14.9
136.1
N.A.
24.5
Ng = Xe        
MP2/6-311+G*
-45.7
114.0
56.6
30.2
MP2/aug-cc-pVTZ
-61.3
106.9
62.7
30.8
CCSD(T)/6-311+G*
-37.2
113.8
N.A.
31.3
CCSD(T)/aug-cc-pVTZ
-51.7
107.4
N.A.
31.7

 

CH3NBArF

單位：Å
R ( Ar-F )
R ( Ar-B )
R ( B-N )
R ( N-C )
R ( C-H )
Ng = Ar          
2.082
1.800
1.246
1.431
1.099
MP2/aug-cc-pVTZ
2.042
1.779
1.238
1.420
1.087
Ng = Kr          
MP2/aug-cc-pVDZ
2.096
1.958
1.250
1.429
1.100
MP2/aug-cc-pVTZ
2.072
1.934
1.242
1.418
1.088

 

單位：kcal/mol
 S-T gap rel. to CH3NB + Ng+ F rel. to CH3NBF + Ng Linear Barrier Bending Barrier
Ng = Ar        
MP2/aug-cc-pVDZ
112.1
-12.8
145.3
12.8
MP2/aug-cc-pVTZ
120.9
-21.5
146.1
13.6
CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ
99.1
-2.8
145.3
13.7
CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVTZ
107.8
-10.5
147.4
14.1
Ng = Kr
MP2/aug-cc-pVDZ
152.2
-35.1
123.1
22.4
MP2/aug-cc-pVTZ
151.9
-33.0
134.6
22.1
CCSD(T)/aug-cc-pVDZ//MP2/aug-cc-pVDZ
137.2
-24.8
123.3
23.1
CCSD(T)/aug-cc-pVTZ//MP2/aug-cc-pVTZ
136.8
-32.7
125.1
22.8

☆aug-cc-pVDZ和aug-cc-pCVDZ之bassis set 差異：多了一組s、p組合。

     ex. F atom

     

OBArF與其線性、bending ts之結構比較

OBNgF分子之結構：

OBNgF→OB+Ng+F反應之線性TS結構：

結論：由各方法來看OBArF線性TS結構之B-Ar鍵及Ar-F鍵會比OBArF分子分別約長0.2~0.3Å及短0.1Å左右。

OBNgF→OBF+Ng之Bending TS 結構：

結論：由各方法來看OBArF的bending ts結構之B-Ar鍵及Ar-F鍵比OBArF分別0.1Å及0.2Å左右。而A(B-Ar-F)鍵角會從原本的180度縮減到約為109度左右。

OBNgF之相對能量比較：