suppmat.doc 104KB Jun 05 2011 09:30:51 PM
Title:
Ethylene Coordination, Insertion and Chain Transfer at a Cationic Aluminum Center: a Comparative Study
with Ab Initio Correlated Level and Density Functional Methods
Author:
Giovanni Talarico*, Peter H. M. Budzelaar and Anton W. Gal
Affiliation:
Department of Inorganic Chemistry, University of Nijmegen, Toernooiveld 1, 6525 ED Nijmegen, The
Netherlands.
Correspondence:
G. Talarico (current address) Dipartimento di Chimica, Università di Napoli, Via Mezzocannone 4, 80134,
Naples, Italy. e-mail: talarico@chemna.dichi.unina.it
Description:
Tables of cartesian coordinates optimized at MP2 level and the total energies computed at CCSD(T) level of all
species mentioned in the text and influence of basis sets (Tables S-I, S-II, S-III, and S-IV).
Table S-I. Selected geometrical parameters a for structures 1-10 calculated with different theoretical methods
Structure
Geometrical
parametersb
HF
MP2
BP86
B3LYP
1
Al-C
Al-H
Al-H
C-H
C-C
Al-C-C
Al-C1
Al-C2
C1-C2
Al-C
Al-H
C-H
Al-C-C
Al-C
Al-C1
Al-C2
C1-C2
C-C
C-C2
Al-H
C-H
Al-C1-C2
C1-Al-C
Al-C1-C2-C
Al-C
Al-H
C-H
Al-H
C-H
Al-C-C
C-C-C
Al-C1
Al-C3
C1-C2
C2-C3
C3-H
C4-H
Al-H
1.941
2.495
3.173
1.089
1.543
115.3
179.8
2.541
2.538
1.337
1.949
2.525
1.089
114.2
144.9
2.089
1.974
2.308
1.454
1.538
2.198
2.201
1.101
83.2
98.2
121.4
6.4
1.941
2.500
1.089
2.716
1.100
112.0
113.0
178.9
2.032
2.032
1.464
1.463
1.294
1.295
2.797
1.929
2.496
3.144
1.098
1.541
114.1
178.7
2.452
2.452
1.352
1.935
2.526
1.097
112.3
144.2
2.062
1.984
2.205
1.439
1.530
2.213
2.220
1.109
78.4
101.6
120.3
9.2
1.929
2.519
1.096
2.126
1.125
101.2
110.5
175.0
2.037
2.037
1.443
1.443
1.291
1.291
2.803
1.947
2.489
3.214
1.106
1.540
116.6
179.4
2.530
2.508
1.348
1.951
2.517
1.106
115.6
148.6
2.105
1.978
2.239
1.452
1.526
2.199
2.194
1.122
79.9
100.1
120.0
7.4
1.951
2.519
1.105
2.152
1.139
103.3
110.6
173.1
2.053
2.053
1.444
1.445
1.307
1.308
2.828
1.937
2.489
3.184
1.099
1.547
115.4
179.9
2.519
2.515
1.350
1.943
2.522
1.100
113.9
145.0
2.095
1.975
2.247
1.453
1.534
2.210
2.214
1.111
80.3
100.4
119.7
7.5
1.940
2.509
1.099
2.218
1.129
104.3
111.2
175.1
2.042
2.042
1.452
1.452
1.312
1.312
2.816
2
TS 3
4
TS 5
1
C1-Al-C3
C2-H-C4
Al-C
Al-C1
C1-C2
C-C
C-H
C1-H
Al-H
Al-H
C-H
C1AlC
C-Al-C1-H
Al-H
Al-C
Al-C
C-C
C-H
Al-C-C
C-Al-H
Al-H-C
Al-C-C-H
Al-H
Al-C1
Al-C2
C1-C2
Al-H
Al-C1
Al-C2
C1-C2
C3-C4
Al-H
Al-N
N-C
N-Al-H
N-Al-N
N-C-N
TS 6
TS 7
8
9
10
a
104.8
168.4
180.0
2.088
2.018
1.342
1.540
1.525
1.458
1.686
2.373
1.096
91.4
174.9
2.2
1.662
2.014
2.318
1.435
1.737
82.7
86.2
86.0
129.6
0.0
1.553
2.500
2.494
1.338
144.2
1.548
2.848
2.847
1.329
1.329
179.9
1.543
1.864
1.319
144.5
71.1
110.6
179.9
103.4
168.3
180.0
2.055
2.014
1.356
1.540
1.528
1.452
1.675
2.419
1.104
92.1
176.0
3.9
1.654
2.020
2.233
1.421
1.727
78.8
88.7
82.6
129.7
0.0
1.559
2.418
2.420
1.354
145.0
1.561
2.638
2.639
1.348
1.349
180.0
1.552
1.880
1.335
144.0
71.7
111.1
179.8
103.3
167.5
179.9
2.083
2.024
1.353
1.537
1.557
1.461
1.693
2.400
1.112
92.5
177.6
1.0
1.663
2.038
2.242
1.423
1.745
78.6
88.9
82.3
130.4
0.0
1.565
2.480
2.476
1.350
148.4
1.566
2.721
2.724
1.342
1.343
180.0
1.559
1.901
1.334
144.6
70.7
111.1
179.9
104.3
167.4
180.0
2.079
2.013
1.356
1.543
1.552
1.453
1.687
2.380
1.106
92.4
176.0
1.6
1.661
2.023
2.261
1.431
1.742
79.8
88.4
83.2
128.3
0.0
1.558
2.468
2.467
1.352
144.7
1.557
2.731
2.731
1.344
1.345
180.0
1.552
1.880
1.335
144.0
71.6
111.0
179.9
In Å and deg. bThe atom numbering scheme is H2C1=CH22 for the olefin and Al-C-C-C for the growing chain.
Table S-II. Basis set influence (at the MP2 level) of olefin coordination and insertion; energies relative to complex [HC(NH)2Al CH2CH3(CH2CH2)]+ (kcal/mol).
EBSSE
Reactant 1a
(complexation)
TS 3
(Insertion)
Product 4
6-31G (d)
6.1
18.9
30.6
-9.0
6-31G (d,p)
6.0
18.6
30.2
-9.7
6-311G (d,p)
4.5
18.4
28.9
-11.2
6-311G (2d,p)
3.6
20.0
28.5
-10.0
Method
a
Corrected for BSSE.
2
Table S-III. Basis set influence (at the MP2 level) on the energies of -hydrogen transfer to the metal (BHE)
relative to precursor [HC(NH)2AlCH2CH3]+ (kcal/mol).
TS 7
(BHE)
Structure 8
Structure 9a
EBSSEb
Structure 10a
EBSSEc
6-31G (d)
39.2
14.1
9.9
5.2
36.9
5.8
6-31G (d,p)
39.8
15.5
10.9
5.1
38.1
5.7
6-311G (d,p)
38.7
16.2
11.2
4.1
38.1
4.1
6-311G (2d,p)
38.7
16.0
8.8
3.3
39.3
3.2
Method
a
Corrected for BSSE; b relative to 9; c relative to 8.
Table S-IV. Basis set influence (at the MP2 level)on the energies of different reactions relative to
[HC(NH)2AlCH2CH3(CH2CH2)]+ in kcal/mol.
E
TS 3
(Insertion)
TS 5
(BHT)
TS 6
(CHT)
TS 7a
(BHE)
6-31G (p)
30.6
24.7
54.1
58.1
5.9
6-31G (d,p)
30.2
23.0
52.0
58.4
7.2
6-311G (d,p)
28.9
21.4
49.1
57.1
7.5
6-311G (2d,p)
28.5
21.2
48.3
58.8
7.3
Method
a
chain growth-chain transfer
Corrected for BSSE.
3
Tables of cartesian coordinates optimized at MP2 level and the total energies computed at
CCSD(T) level of all species mentioned in the text.
Ethylene
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 C
2
2 C
1
1.334903( 1)
3
3 H
1
1.084765( 2)
2 121.704( 6)
4
4 H
1
1.084765( 3)
2 121.704( 7)
3 180.000( 10)
0
5
5 H
2
1.084765( 4)
1 121.704( 8)
3 180.000( 11)
0
6
6 H
2
1.084765( 5)
1 121.704( 9)
5 180.000( 12)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
6
0.000000
0.000000
0.667451
2
6
0.000000
0.000000
-0.667451
3
1
0.000000
0.922890
1.237530
4
1
0.000000
-0.922890
1.237530
5
1
0.000000
-0.922890
-1.237530
6
1
0.000000
0.922890
-1.237530
---------------------------------------------------------DD1Dir will call FoFMem
1 times, MxPair=
42
NAB=
21 NAA=
0 NBB=
0.
The Euclidean norm of the A-vectors is
0.3131148D-05
DE(CORR)= -0.28156041D+00
E(CORR)=
-0.78312630072D+02
NORM(A)=
0.10617637D+01
Dominant configurations:
***********************
Spin Case
I
J
A
B
Value
ABAB
8
8
9
9
-0.146796D+00
Largest amplitude= 1.47D-01
T4(AAA)= -0.16102092D-03
T4(AAB)= -0.47131497D-02
T5(AAA)= 0.12209276D-04
T5(AAB)= 0.23060927D-03
Time for triples=
16.96 seconds.
T4(CCSD)= -0.97483413D-02
T5(CCSD)= 0.48563708D-03
CCSD(T)= -0.78321892777D+02
4
Reactant 1
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 N
1
1.891674( 1)
3
3 H
2
1.013008( 2)
1 149.717( 14)
4
4 C
2
1.333918( 3)
3 121.463( 15)
1 179.358( 26)
0
5
5 H
4
1.090398( 4)
2 124.369( 16)
1 180.240( 27)
0
6
6 N
4
1.333545( 5)
2 111.243( 17)
3 -179.616( 28)
0
7
7 H
6
1.013044( 6)
4 121.543( 18)
2 180.161( 29)
0
8
8 C
1
1.928967( 7)
2 143.206( 19)
4 179.129( 30)
0
9
9 C
8
1.540758( 8)
1 114.093( 20)
2
-7.053( 31)
0
10 10 H
8
1.097322( 9)
9 110.571( 21)
1 121.658( 32)
0
11 11 H
8
1.097400( 10)
9 110.557( 22)
1 -121.889( 33)
0
12 12 H
9
1.092452( 11)
8 112.066( 23) 11 177.226( 34)
0
13 13 H
9
1.092423( 12)
8 112.058( 24) 10 -177.498( 35)
0
14 14 H
9
1.091995( 13)
8 109.686( 25) 13 119.138( 36)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
0.002342
-0.259330
-0.030184
2
7
1.231135
1.178874
-0.038359
3
1
1.411494
2.175191
-0.070077
4
6
2.226355
0.292739
0.021973
5
1
3.284101
0.556042
0.050522
6
7
1.760208
-0.956435
0.046732
7
1
2.383295
-1.753758
0.094661
8
6
-1.879162
-0.683686
-0.058124
9
6
-2.802591
0.543194
0.068293
10
1
-2.073454
-1.397632
0.752214
11
1
-2.088957
-1.229839
-0.986558
12
1
-2.647926
1.078169
1.008149
13
1
-2.659933
1.250301
-0.752094
14
1
-3.846079
0.222258
0.044106
---------------------------------------------------------DD1Dir will call FoFDir
1 times, MxPair=
272
NAB=
136 NAA=
0 NBB=
0.
Spin AB IR= 101 I=
9 J=
9 Mu=
42 Nu=
42 IOp=1 MuP=
42 NuP=
FactIJ= 0.0 Fact= 0.0 A=-3.5498618990D-01 AP=-3.5498618990D-01
The Euclidean norm of the A-vectors is
0.5444416D-05
DE(CORR)= -0.79899121D+00
E(CORR)=
-0.46970357664D+03
NORM(A)=
0.11463756D+01
Largest amplitude= 6.48D-02
T4(AAA)= -0.67798456D-03
T4(AAB)= -0.13157990D-01
T5(AAA)= 0.46312804D-04
T5(AAB)= 0.73750443D-03
Time for triples=
5294.96 seconds.
T4(CCSD)= -0.27671948D-01
T5(CCSD)= 0.15676345D-02
CCSD(T)= -0.46972968095D+03
42
5
-complex 2
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
1.934515( 1)
3
3 H
2
1.097569( 2)
1 109.748( 22)
4
4 H
2
1.097586( 3)
1 109.705( 23)
3 -115.453( 42)
0
5
5 C
2
1.541156( 4)
1 112.348( 24)
3 122.322( 43)
0
6
6 H
5
1.093321( 5)
2 111.786( 25)
4 177.321( 44)
0
7
7 H
5
1.093313( 6)
2 111.783( 26)
3 -177.068( 45)
0
8
8 H
5
1.092621( 7)
2 110.662( 27)
7 119.503( 46)
0
9
9 N
1
1.914328( 8)
2 132.140( 28)
4
72.535( 47)
0
10 10 C
9
1.331874( 9)
1
89.188( 29)
2 127.943( 48)
0
11 11 N
10
1.332112( 10)
1
55.697( 30)
9 -176.611( 49)
0
12 12 H
9
1.012748( 11)
1 149.778( 31) 10 -170.264( 50)
0
13 13 H
10
1.091092( 12)
9 124.356( 32)
1 -177.173( 51)
0
14 14 H
11
1.012731( 13) 10 120.592( 33)
9 -177.578( 52)
0
15
X
1
2.356851( 14)
2 109.037( 34)
5 -178.496( 53)
0
16 15 C
15
0.676532( 15)
1
90.005( 35)
2 -89.033( 54)
0
17
X
15
1.000000( 16) 16
90.000( 36)
1
0.000( 55)
0
18 16 C
15
0.676532( 17) 17
90.000( 37) 16 180.000( 56)
0
19 17 H
16
1.085671( 18) 18 121.224( 38)
1 -98.071( 57)
0
20 18 H
16
1.088460( 19) 18 121.272( 39) 19 -174.282( 58)
0
21 19 H
18
1.088516( 20) 16 121.266( 40) 19 174.351( 59)
0
22 20 H
18
1.085621( 21) 19
95.379( 41) 21 -171.010( 60)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
0.095074
-0.077423
-0.007604
2
6
1.839091
-0.914495
-0.015470
3
1
1.938406
-1.556312
-0.900267
4
1
1.930321
-1.587784
0.846536
5
6
2.984146
0.116718
0.009228
6
1
2.954201
0.777255
-0.861487
7
1
2.947774
0.742007
0.905344
8
1
3.954844
-0.384803
0.002736
9
7
-0.670441
1.285601
1.097297
10
6
-1.012538
1.957135
-0.000839
11
7
-0.694162
1.279335
-1.102541
12
1
-0.812768
1.691462
2.014181
13
1
-1.494749
2.935884
0.001106
14
1
-0.859439
1.677958
-2.018733
15
6
-1.558473
-1.764619
-0.664759
16
6
-1.565430
-1.742026
0.688098
17
1
-2.300879
-1.220574
-1.240545
18
1
-0.867714
-2.400285
-1.215692
19
1
-0.879655
-2.358069
1.266951
20
1
-2.314859
-1.181070
1.237878
---------------------------------------------------------DD1Dir will call FoFDir
1 times, MxPair=
506
NAB=
253 NAA=
0 NBB=
0.
Spin AB IR= 199 I= 13 J= 13 Mu=
80 Nu=
80 IOp=1 MuP=
80 NuP=
FactIJ= 0.0 Fact= 0.0 A=-4.6532834924D-01 AP=-4.6532834924D-01
The Euclidean norm of the A-vectors is
0.7995369D-05
DE(CORR)= -0.10873041D+01
E(CORR)=
-0.54805067865D+03
NORM(A)=
0.11990484D+01
Largest amplitude= 6.75D-02
T4(AAA)= -0.93831506D-03
T4(AAB)= -0.18510157D-01
T5(AAA)= 0.59723962D-04
T5(AAB)= 0.94510047D-03
Time for triples=
39574.64 seconds.
T4(CCSD)= -0.38896945D-01
T5(CCSD)= 0.20096489D-02
CCSD(T)= -0.54808756595D+03
80
6
TS 3 (insertion)
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
2.295057( 1)
3
3 N
2
1.333225( 2)
1
55.640( 20)
4
4 N
2
1.331391( 3)
3 111.618( 21)
1
-1.950( 38)
0
5
5 H
2
1.090439( 4)
3 124.105( 22)
4 180.149( 39)
0
6
6 H
3
1.012121( 5)
2 120.827( 23)
4 181.440( 40)
0
7
7 H
4
1.012346( 6)
2 120.743( 24)
3 -181.461( 41)
0
8
8 C
1
2.061399( 7)
3 111.386( 25)
2 112.566( 42)
0
9
9 C
8
1.530122( 8)
1 109.951( 26)
6
34.848( 43)
0
10 10 H
8
1.109545( 9)
9 111.160( 27)
1
90.189( 44)
0
11 11 H
8
1.088880( 10)
9 111.527( 28)
1 -155.107( 45)
0
12 12 H
9
1.093268( 11)
8 111.558( 29) 10 181.859( 46)
0
13 13 H
9
1.093052( 12)
8 112.710( 30) 12 -121.648( 47)
0
14 14 H
9
1.093612( 13)
8 109.982( 31) 12 118.790( 48)
0
15 15 C
1
2.204499( 14)
8
62.385( 32) 10 147.492( 49)
0
16 16 C
15
1.438190( 15)
1
61.865( 33)
8 169.981( 50)
0
17 17 H
15
1.087248( 16) 16 118.883( 34)
1 -101.005( 51)
0
18 18 H
15
1.085696( 17) 16 120.640( 35)
1 108.031( 52)
0
19 19 H
16
1.088578( 18) 15 116.316( 36) 18 -142.971( 53)
0
20 20 H
16
1.088778( 19) 15 116.475( 37) 17 148.779( 54)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
-0.207037
0.344970
-0.020178
2
6
-2.394577
-0.349258
-0.022028
3
7
-1.497352
-0.686413
-0.948744
4
7
-1.854808
0.408108
0.930678
5
1
-3.440036
-0.658562
-0.042070
6
1
-1.763955
-1.244207
-1.750103
7
1
-2.419495
0.761232
1.693093
8
6
1.261648
-0.847931
0.797940
9
6
1.723308
-1.885233
-0.227802
10
1
0.419818
-1.235245
1.408186
11
1
2.034886
-0.645658
1.537433
12
1
2.574082
-1.522620
-0.810838
13
1
0.932148
-2.168721
-0.926704
14
1
2.046387
-2.797071
0.282255
15
6
1.827839
1.181163
0.120801
16
6
0.847391
1.907507
-0.640472
17
1
2.062833
1.514764
1.128569
18
1
2.637071
0.655942
-0.377217
19
1
0.491239
2.839227
-0.204518
20
1
0.987965
1.926943
-1.719962
---------------------------------------------------------DE(CORR)= -0.10956877D+01
E(CORR)=
NORM(A)=
0.12017481D+01
Largest amplitude= 5.13D-02
T4(AAA)= -0.10651453D-02
T4(AAB)= -0.19739589D-01
T5(AAA)= 0.68748974D-04
T5(AAB)= 0.11336342D-02
Time for triples=
31871.47 seconds.
T4(CCSD)= -0.41609469D-01
T5(CCSD)= 0.24047663D-02
CCSD(T)= -0.54803741168D+03
-0.54799820698D+03
7
Product 4
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 N
1
1.895702( 1)
3
3 H
2
1.012714( 2)
1 149.667( 20)
4
4 C
2
1.333397( 3)
3 121.343( 21)
1 182.582( 38)
0
5
5 H
4
1.090527( 4)
2 124.314( 22)
1 181.091( 39)
0
6
6 N
4
1.332456( 5)
2 111.320( 23)
3 -180.221( 40)
0
7
7 H
6
1.012763( 6)
4 121.241( 24)
2 180.999( 41)
0
8
8 C
1
1.929450( 7)
2 145.499( 25)
4 -188.688( 42)
0
9
9 C
8
1.543353( 8)
1 101.225( 26)
2 115.795( 43)
0
10 10 H
8
1.096526( 9)
9 110.863( 27)
1 116.273( 44)
0
11 11 H
8
1.093646( 10)
9 112.944( 28)
1 -123.624( 45)
0
12 12 H
9
1.095784( 11)
8 110.214( 29) 11 -38.435( 46)
0
13 13 H
9
1.094680( 12)
8 110.953( 30) 10 -40.610( 47)
0
14 14 C
9
1.528807( 13)
8 110.504( 31) 13 121.357( 48)
0
15 15 H
14
1.124525( 14)
9 109.295( 32) 13 -178.534( 49)
0
16 16 H
14
1.098727( 15)
9 109.726( 33) 12 181.190( 50)
0
17 17 C
14
1.523621( 16)
9 114.956( 34) 15 118.929( 51)
0
18 18 H
17
1.092587( 17) 14 109.529( 35) 15 -177.520( 52)
0
19 19 H
17
1.091710( 18) 14 111.549( 36) 18 119.589( 53)
0
20 20 H
17
1.092283( 19) 14 110.849( 37) 18 -119.342( 54)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
0.725852
0.577823
-0.033618
2
7
2.089184
-0.250857
-1.057483
3
1
2.519920
-0.431565
-1.956038
4
6
2.616884
-0.723385
0.072207
5
1
3.524015
-1.326631
0.121762
6
7
1.893878
-0.363845
1.132127
7
1
2.168293
-0.630085
2.069944
8
6
-0.766593
1.800247
-0.066208
9
6
-1.935186
0.857240
0.290260
10
1
-0.887831
2.207480
-1.077065
11
1
-0.683478
2.652277
0.614379
12
1
-2.024729
0.759736
1.378018
13
1
-2.887397
1.261033
-0.068306
14
6
-1.712145
-0.526433
-0.320439
15
1
-0.747131
-0.953090
0.068490
16
1
-1.599730
-0.437281
-1.409758
17
6
-2.786886
-1.555119
0.008436
18
1
-3.748442
-1.217391
-0.385386
19
1
-2.561498
-2.526538
-0.435835
20
1
-2.885944
-1.682028
1.088790
---------------------------------------------------------DE(CORR)= -0.10887892D+01
E(CORR)=
NORM(A)=
0.11940110D+01
Largest amplitude= 4.94D-02
T4(AAA)= -0.97112351D-03
T4(AAB)= -0.17978105D-01
T5(AAA)= 0.57810712D-04
T5(AAB)= 0.89721687D-03
Time for triples=
40030.42 seconds.
T4(CCSD)= -0.37898457D-01
T5(CCSD)= 0.19100552D-02
CCSD(T)= -0.54809954261D+03
-0.54806355421D+03
8
TS 5 (BHT)
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
2.325295( 1)
3
3 N
2
1.330950( 2)
1
55.816( 20)
4
4 N
2
1.330971( 3)
3 111.628( 21)
1
0.003( 38)
0
5
5 H
2
1.091224( 4)
3 124.186( 22)
4 -179.999( 39)
0
6
6 H
3
1.011984( 5)
2 120.196( 23)
4 180.000( 40)
0
7
7 H
4
1.011985( 6)
2 120.197( 24)
3 -179.993( 41)
0
8
8 C
1
2.036598( 7)
2 128.333( 25)
3
89.977( 42)
0
9
9 C
8
1.442251( 8)
1 115.784( 26)
4 138.301( 43)
0
10 10 H
8
1.093762( 9)
9 113.286( 27)
1 -116.091( 44)
0
11 11 H
8
1.093798( 10)
9 113.281( 28) 10 -127.827( 45)
0
12 12 H
9
1.090867( 11)
8 118.000( 29) 11 -134.701( 46)
0
13 13 H
9
1.090902( 12)
8 117.993( 30) 10 134.790( 47)
0
14 14 H
9
1.291127( 13)
8 108.434( 31) 11 116.132( 48)
0
15 15 C
1
2.036608( 14)
4 120.565( 32)
7
65.631( 49)
0
16 16 C
15
1.442206( 15) 14
33.499( 33)
1 -180.095( 50)
0
17 17 H
15
1.093715( 16) 16 113.288( 34) 14 -116.004( 51)
0
18 18 H
15
1.093772( 17) 16 113.281( 35) 17 -127.830( 52)
0
19 19 H
16
1.090847( 18) 15 118.002( 36) 18 -134.669( 53)
0
20 20 H
16
1.090868( 19) 15 117.987( 37) 17 134.820( 54)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
-0.336740
-0.000024
-0.000124
2
6
-2.662035
0.000011
0.000093
3
7
-1.914127
0.000033
1.101030
4
7
-1.914268
-0.000093
-1.100965
5
1
-3.753259
0.000089
0.000155
6
1
-2.351627
0.000114
2.013558
7
1
-2.351876
-0.000008
-2.013440
8
6
0.926403
-1.597585
0.000447
9
6
2.334204
-1.284241
-0.000530
10
1
0.600805
-2.122131
0.903305
11
1
0.599927
-2.123396
-0.901401
12
1
2.903459
-1.481723
0.908832
13
1
2.902078
-1.481656
-0.910813
14
1
2.466597
0.000080
-0.000521
15
6
0.926364
1.597581
-0.000553
16
6
2.334129
1.284289
0.000620
17
1
0.600925
2.122353
-0.903280
18
1
0.599677
2.123059
0.901382
19
1
2.903696
1.482581
-0.908348
20
1
2.901585
1.481035
0.911266
---------------------------------------------------------DE(CORR)= -0.10975322D+01
E(CORR)=
NORM(A)=
0.12063145D+01
Largest amplitude= 7.92D-02
T4(AAA)= -0.11447073D-02
T4(AAB)= -0.20291923D-01
T5(AAA)= 0.60916811D-04
T5(AAB)= 0.12846929D-02
Time for triples=
30544.22 seconds.
T4(CCSD)= -0.42873260D-01
T5(CCSD)= 0.26912194D-02
CCSD(T)= -0.54804701675D+03
-0.54800683470D+03
9
TS 6 (CHT)
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
2.289492( 1)
3
3 N
2
1.333169( 2)
1
55.734( 20)
4
4 N
2
1.332019( 3)
3 111.557( 21)
1
1.403( 38)
0
5
5 H
2
1.090245( 4)
3 124.195( 22)
4 -180.029( 39)
0
6
6 H
3
1.012233( 5)
2 121.032( 23)
4 179.393( 40)
0
7
7 H
4
1.012343( 6)
2 121.062( 24)
3 -179.168( 41)
0
8
8 C
1
2.055119( 7)
2 131.609( 25)
3
86.285( 42)
0
9
9 C
8
1.540563( 8)
1 108.381( 26)
3 -29.017( 43)
0
10 10 H
8
1.099746( 9)
1 128.409( 27)
4 109.636( 44)
0
11 11 H
8
1.102800( 10)
9 112.024( 28) 10 112.611( 45)
0
12 12 H
9
1.093485( 11)
8 111.284( 29) 11 -180.668( 46)
0
13 13 H
9
1.092749( 12)
8 112.147( 30) 12 121.033( 47)
0
14 14 H
9
1.092367( 13)
8 110.539( 31) 13 119.925( 48)
0
15 15 C
1
2.014515( 14)
4 123.930( 32)
2 -123.754( 49)
0
16 16 C
15
1.356055( 15)
1 119.881( 33)
4 142.832( 50)
0
17 17 H
15
1.090591( 16) 16 117.859( 34)
1 163.030( 51)
0
18 18 H
16
1.089955( 17) 15 121.890( 35) 17 183.760( 52)
0
19 19 H
16
1.088000( 18) 15 122.907( 36) 18 179.055( 53)
0
20 20 H
1
1.675007( 19)
4 140.694( 37)
2 177.469( 54)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
0.214580
-0.167061
-0.231476
2
6
2.432054
-0.058787
0.327860
3
7
1.431217
0.162063
1.180438
4
7
1.981824
-0.321037
-0.898024
5
1
3.487228
-0.027967
0.600428
6
1
1.611636
0.366379
2.155281
7
1
2.620601
-0.523150
-1.656940
8
6
-1.112951
1.281086
-0.834837
9
6
-1.438116
2.176772
0.375680
10
1
-2.019459
1.164841
-1.446534
11
1
-0.414878
1.769545
-1.535031
12
1
-2.139783
1.685803
1.055623
13
1
-0.543788
2.438757
0.946331
14
1
-1.903457
3.109312
0.048432
15
6
-1.176959
-1.615132
-0.389525
16
6
-2.050317
-1.826574
0.626066
17
1
-1.063454
-2.401896
-1.136189
18
1
-2.259935
-1.061817
1.373868
19
1
-2.601345
-2.756787
0.747788
20
1
-1.376453
-0.222599
-0.752223
---------------------------------------------------------DE(CORR)= -0.10999708D+01
E(CORR)=
NORM(A)=
0.12042885D+01
Largest amplitude= 7.31D-02
T4(AAA)= -0.10315790D-02
T4(AAB)= -0.19988196D-01
T5(AAA)= 0.63055603D-04
T5(AAB)= 0.10399748D-02
Time for triples=
40486.87 seconds.
T4(CCSD)= -0.42039549D-01
T5(CCSD)= 0.22060608D-02
CCSD(T)= -0.54799913447D+03
-0.54795930098D+03
10
TS 7 (BHE)
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
2.280567( 1)
3
3 N
2
1.332497( 2)
1
55.846( 14)
4
4 N
2
1.332448( 3)
3 111.705( 15)
1
-0.739( 26)
0
5
5 H
2
1.090007( 4)
3 124.146( 16)
4 -179.961( 27)
0
6
6 H
3
1.012236( 5)
2 121.303( 17)
4 180.566( 28)
0
7
7 H
4
1.012172( 6)
2 121.357( 18)
3 -180.382( 29)
0
8
8 C
1
2.020224( 7)
2 141.541( 19)
4
89.840( 30)
0
9
9 C
8
1.421860( 8)
1
78.802( 20)
4 -131.187( 31)
0
10 10 H
8
1.087993( 9)
9 117.084( 21)
1 -108.026( 32)
0
11 11 H
8
1.088346( 10)
9 117.091( 22) 10 -144.102( 33)
0
12 12 H
9
1.087381( 11)
8 121.129( 23) 10 151.087( 34)
0
13 13 H
9
1.087419( 12)
8 121.105( 24) 11 -151.167( 35)
0
14 14 H
1
1.655026( 13)
3 121.442( 25)
6
62.068( 36)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
-0.165616
-0.002285
-0.193289
2
6
2.098828
0.001909
0.077382
3
7
1.353090
1.103193
-0.003832
4
7
1.357427
-1.102296
-0.003081
5
1
3.182382
0.004091
0.195794
6
1
1.770273
2.024733
0.032813
7
1
1.777048
-2.022521
0.036858
8
6
-1.885507
0.000517
0.866554
9
6
-2.382172
0.000233
-0.465741
10
1
-1.994477
-0.920104
1.436038
11
1
-1.989868
0.923207
1.434225
12
1
-2.742139
0.914413
-0.931676
13
1
-2.745412
-0.913722
-0.929663
14
1
-1.065313
-0.002631
-1.582409
---------------------------------------------------------DD1Dir will call FoFDir
1 times, MxPair=
272
NAB=
136 NAA=
0 NBB=
0.
Spin AB IR= 116 I= 11 J= 11 Mu=
25 Nu=
25 IOp=1 MuP=
25 NuP=
FactIJ= 0.0 Fact= 0.0 A=-5.8784089079D-01 AP=-5.8784089079D-01
The Euclidean norm of the A-vectors is
0.7921390D-05
DE(CORR)= -0.80144047D+00
E(CORR)=
-0.46964188144D+03
NORM(A)=
0.11528126D+01
Largest amplitude= 4.77D-02
T4(AAA)= -0.76629002D-03
T4(AAB)= -0.14404643D-01
T5(AAA)= 0.54027398D-04
T5(AAB)= 0.92636733D-03
Time for triples=
5133.25 seconds.
T4(CCSD)= -0.30341866D-01
T5(CCSD)= 0.19607895D-02
CCSD(T)= -0.46967026252D+03
25
11
Structure 8
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
2.306458( 1)
3
3 N
2
1.332523( 2)
1
55.656( 16)
4
4 N
2
1.332393( 3)
3 111.254( 17)
1
-2.973( 30)
0
5
5 H
2
1.090741( 4)
3 124.357( 18)
4 180.106( 31)
0
6
6 H
3
1.012754( 5)
2 120.861( 19)
4 182.620( 32)
0
7
7 H
4
1.012765( 6)
2 120.864( 20)
3 -182.674( 33)
0
8
8 H
1
1.559433( 7)
2 144.998( 21)
3
91.890( 34)
0
9
X
1
2.322742( 8)
8 105.607( 22)
3 128.321( 35)
0
10
9 C
9
0.677134( 9)
1
90.101( 23)
8 -89.294( 36)
0
11
X
9
1.000000( 10) 10
90.000( 24)
1
0.000( 37)
0
12 10 C
9
0.677134( 11) 11
90.000( 25) 10 180.000( 38)
0
13 11 H
10
1.085885( 12) 12 121.199( 26)
1 -99.082( 39)
0
14 12 H
10
1.089198( 13) 12 121.249( 27) 13 -174.186( 40)
0
15 13 H
12
1.089290( 14) 10 121.241( 28) 13 174.140( 41)
0
16 14 H
12
1.085835( 15) 10 121.211( 29) 15 -174.039( 42)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
-0.054830
-0.005857
0.854284
2
6
1.799969
0.001565
-0.516634
3
7
1.175337
-1.100394
-0.102941
4
7
1.177494
1.099129
-0.088674
5
1
2.703135
0.004380
-1.128188
6
1
1.547741
-2.018494
-0.312890
7
1
1.552045
2.019176
-0.285949
8
1
-0.550385
-0.011841
2.332871
9
6
-1.984684
-0.672037
-0.446127
10
6
-1.970101
0.682140
-0.452036
11
1
-1.597479
-1.242410
-1.285111
12
1
-2.468448
-1.228395
0.355616
13
1
-2.442414
1.255687
0.344529
14
1
-1.572337
1.236885
-1.296477
---------------------------------------------------------DD1Dir will call FoFDir
1 times, MxPair=
272
NAB=
136 NAA=
0 NBB=
0.
Spin AB IR= 116 I= 11 J= 11 Mu=
25 Nu=
25 IOp=1 MuP=
25 NuP=
FactIJ= 0.0 Fact= 0.0 A=-4.4940089897D-01 AP=-4.4940089897D-01
The Euclidean norm of the A-vectors is
0.4715827D-05
DE(CORR)= -0.79894981D+00
E(CORR)=
-0.46968210595D+03
NORM(A)=
0.11513837D+01
Largest amplitude= 5.49D-02
T4(AAA)= -0.71205693D-03
T4(AAB)= -0.14028945D-01
T5(AAA)= 0.49145168D-04
T5(AAB)= 0.77126737D-03
Time for triples=
5105.30 seconds.
T4(CCSD)= -0.29482004D-01
T5(CCSD)= 0.16408251D-02
CCSD(T)= -0.46970994713D+03
25
12
Structure 9
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
2.318399( 1)
3
3 N
2
1.331648( 2)
1
55.576( 24)
4
4 N
2
1.331678( 3)
3 111.155( 25)
1
-0.009( 46)
0
5
5 H
2
1.090815( 4)
3 124.413( 26)
4 180.001( 47)
0
6
6 H
3
1.012840( 5)
2 120.854( 27)
4 180.005( 48)
0
7
7 H
4
1.012850( 6)
2 120.837( 28)
3 -180.003( 49)
0
8
8 H
1
1.560808( 7)
2 179.952( 29)
3 -188.226( 50)
0
9
X
1
2.551389( 8)
8
88.104( 30)
3
89.957( 51)
0
10
9 C
9
0.674040( 9)
1
89.981( 31)
8 -89.992( 52)
0
11
X
9
1.000000( 10) 10
90.000( 32)
1
0.000( 53)
0
12 10 C
9
0.674040( 11) 11
90.000( 33) 10 180.000( 54)
0
13 11 H
10
1.084237( 12) 12 121.278( 34)
1 -104.131( 55)
0
14 12 H
10
1.087232( 13) 12 121.444( 35) 13 -174.058( 56)
0
15 13 H
12
1.087227( 14) 10 121.451( 36) 13 174.087( 57)
0
16 14 H
12
1.084240( 15) 10 121.279( 37) 15 -174.179( 58)
0
17
X
1
2.551031( 16)
8
88.093( 38)
3 -89.954( 59)
0
18 15 C
17
0.674043( 17)
1
89.973( 39)
8
89.984( 60)
0
19
X
17
1.000000( 18) 18
90.000( 40)
1
0.000( 61)
0
20 16 C
17
0.674043( 19) 19
90.000( 41) 18 180.000( 62)
0
21 17 H
18
1.084237( 20) 20 121.277( 42)
1 104.183( 63)
0
22 18 H
18
1.087236( 21) 20 121.443( 43) 21 174.031( 64)
0
23 19 H
20
1.084244( 22) 18 121.278( 44) 22 174.108( 65)
0
24 20 H
20
1.087228( 23) 18 121.452( 45) 23 -174.159( 66)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
-0.000050
-0.563158
-0.002092
2
6
-0.000201
1.755236
0.002946
3
7
0.000032
1.000046
1.099747
4
7
-0.000138
1.004870
-1.097199
5
1
-0.000404
2.846048
0.005536
6
1
-0.000060
1.421631
2.020677
7
1
-0.000346
1.430778
-2.016148
8
1
-0.000136
-2.123960
-0.006780
9
6
2.549199
-0.649817
0.673632
10
6
2.550676
-0.645585
-0.674441
11
1
2.804459
0.239039
1.239624
12
1
2.386109
-1.564824
1.237757
13
1
2.388390
-1.556875
-1.244769
14
1
2.805738
0.247205
-1.234304
15
6
-2.548806
-0.650102
0.673727
16
6
-2.550539
-0.645701
-0.674351
17
1
-2.804843
0.238435
1.239869
18
1
-2.385130
-1.565104
1.237698
19
1
-2.806831
0.246847
-1.234044
20
1
-2.387531
-1.556765
-1.244839
---------------------------------------------------------DE(CORR)= -0.10892501D+01
E(CORR)=
NORM(A)=
0.12058560D+01
Largest amplitude= 6.09D-02
T4(AAA)= -0.96958325D-03
T4(AAB)= -0.19599966D-01
T5(AAA)= 0.62690319D-04
T5(AAB)= 0.10007197D-02
Time for triples=
31954.60 seconds.
T4(CCSD)= -0.41139099D-01
T5(CCSD)= 0.21268201D-02
CCSD(T)= -0.54804372746D+03
-0.54800471518D+03
13
Structure 10
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
2.279010( 1)
3
3 N
2
1.334747( 2)
1
55.565( 8)
4
4 N
2
1.335142( 3)
3 111.110( 9)
1
-0.010( 14)
0
5
5 H
2
1.090040( 4)
3 124.453( 10)
4 179.995( 15)
0
6
6 H
3
1.013450( 5)
2 121.872( 11)
4 179.956( 16)
0
7
7 H
4
1.013430( 6)
2 121.875( 12)
3 -180.062( 17)
0
8
8 H
1
1.552160( 7)
3 143.960( 13)
2 180.006( 18)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
1.099682
-0.000794
0.000021
2
6
-1.179328
0.000605
0.000033
3
7
-0.423887
1.100995
0.000065
4
7
-0.424645
-1.100785
-0.000219
5
1
-2.269368
0.000926
0.000263
6
1
-0.830552
2.029275
-0.000416
7
1
-0.832089
-2.028702
0.000660
8
1
2.651835
0.003724
0.000106
---------------------------------------------------------DD1Dir will call FoFMem
1 times, MxPair=
110
NAB=
55 NAA=
0 NBB=
0.
The Euclidean norm of the A-vectors is
0.4974486D-05
DE(CORR)= -0.51164566D+00
E(CORR)=
-0.39132909977D+03
NORM(A)=
0.10964382D+01
Largest amplitude= 6.60D-02
T4(AAA)= -0.46563710D-03
T4(AAB)= -0.87034305D-02
T5(AAA)= 0.35542099D-04
T5(AAB)= 0.55224452D-03
Time for triples=
301.27 seconds.
T4(CCSD)= -0.18338135D-01
T5(CCSD)= 0.11755732D-02
CCSD(T)= -0.39134626234D+03
14
Ethylene Coordination, Insertion and Chain Transfer at a Cationic Aluminum Center: a Comparative Study
with Ab Initio Correlated Level and Density Functional Methods
Author:
Giovanni Talarico*, Peter H. M. Budzelaar and Anton W. Gal
Affiliation:
Department of Inorganic Chemistry, University of Nijmegen, Toernooiveld 1, 6525 ED Nijmegen, The
Netherlands.
Correspondence:
G. Talarico (current address) Dipartimento di Chimica, Università di Napoli, Via Mezzocannone 4, 80134,
Naples, Italy. e-mail: talarico@chemna.dichi.unina.it
Description:
Tables of cartesian coordinates optimized at MP2 level and the total energies computed at CCSD(T) level of all
species mentioned in the text and influence of basis sets (Tables S-I, S-II, S-III, and S-IV).
Table S-I. Selected geometrical parameters a for structures 1-10 calculated with different theoretical methods
Structure
Geometrical
parametersb
HF
MP2
BP86
B3LYP
1
Al-C
Al-H
Al-H
C-H
C-C
Al-C-C
Al-C1
Al-C2
C1-C2
Al-C
Al-H
C-H
Al-C-C
Al-C
Al-C1
Al-C2
C1-C2
C-C
C-C2
Al-H
C-H
Al-C1-C2
C1-Al-C
Al-C1-C2-C
Al-C
Al-H
C-H
Al-H
C-H
Al-C-C
C-C-C
Al-C1
Al-C3
C1-C2
C2-C3
C3-H
C4-H
Al-H
1.941
2.495
3.173
1.089
1.543
115.3
179.8
2.541
2.538
1.337
1.949
2.525
1.089
114.2
144.9
2.089
1.974
2.308
1.454
1.538
2.198
2.201
1.101
83.2
98.2
121.4
6.4
1.941
2.500
1.089
2.716
1.100
112.0
113.0
178.9
2.032
2.032
1.464
1.463
1.294
1.295
2.797
1.929
2.496
3.144
1.098
1.541
114.1
178.7
2.452
2.452
1.352
1.935
2.526
1.097
112.3
144.2
2.062
1.984
2.205
1.439
1.530
2.213
2.220
1.109
78.4
101.6
120.3
9.2
1.929
2.519
1.096
2.126
1.125
101.2
110.5
175.0
2.037
2.037
1.443
1.443
1.291
1.291
2.803
1.947
2.489
3.214
1.106
1.540
116.6
179.4
2.530
2.508
1.348
1.951
2.517
1.106
115.6
148.6
2.105
1.978
2.239
1.452
1.526
2.199
2.194
1.122
79.9
100.1
120.0
7.4
1.951
2.519
1.105
2.152
1.139
103.3
110.6
173.1
2.053
2.053
1.444
1.445
1.307
1.308
2.828
1.937
2.489
3.184
1.099
1.547
115.4
179.9
2.519
2.515
1.350
1.943
2.522
1.100
113.9
145.0
2.095
1.975
2.247
1.453
1.534
2.210
2.214
1.111
80.3
100.4
119.7
7.5
1.940
2.509
1.099
2.218
1.129
104.3
111.2
175.1
2.042
2.042
1.452
1.452
1.312
1.312
2.816
2
TS 3
4
TS 5
1
C1-Al-C3
C2-H-C4
Al-C
Al-C1
C1-C2
C-C
C-H
C1-H
Al-H
Al-H
C-H
C1AlC
C-Al-C1-H
Al-H
Al-C
Al-C
C-C
C-H
Al-C-C
C-Al-H
Al-H-C
Al-C-C-H
Al-H
Al-C1
Al-C2
C1-C2
Al-H
Al-C1
Al-C2
C1-C2
C3-C4
Al-H
Al-N
N-C
N-Al-H
N-Al-N
N-C-N
TS 6
TS 7
8
9
10
a
104.8
168.4
180.0
2.088
2.018
1.342
1.540
1.525
1.458
1.686
2.373
1.096
91.4
174.9
2.2
1.662
2.014
2.318
1.435
1.737
82.7
86.2
86.0
129.6
0.0
1.553
2.500
2.494
1.338
144.2
1.548
2.848
2.847
1.329
1.329
179.9
1.543
1.864
1.319
144.5
71.1
110.6
179.9
103.4
168.3
180.0
2.055
2.014
1.356
1.540
1.528
1.452
1.675
2.419
1.104
92.1
176.0
3.9
1.654
2.020
2.233
1.421
1.727
78.8
88.7
82.6
129.7
0.0
1.559
2.418
2.420
1.354
145.0
1.561
2.638
2.639
1.348
1.349
180.0
1.552
1.880
1.335
144.0
71.7
111.1
179.8
103.3
167.5
179.9
2.083
2.024
1.353
1.537
1.557
1.461
1.693
2.400
1.112
92.5
177.6
1.0
1.663
2.038
2.242
1.423
1.745
78.6
88.9
82.3
130.4
0.0
1.565
2.480
2.476
1.350
148.4
1.566
2.721
2.724
1.342
1.343
180.0
1.559
1.901
1.334
144.6
70.7
111.1
179.9
104.3
167.4
180.0
2.079
2.013
1.356
1.543
1.552
1.453
1.687
2.380
1.106
92.4
176.0
1.6
1.661
2.023
2.261
1.431
1.742
79.8
88.4
83.2
128.3
0.0
1.558
2.468
2.467
1.352
144.7
1.557
2.731
2.731
1.344
1.345
180.0
1.552
1.880
1.335
144.0
71.6
111.0
179.9
In Å and deg. bThe atom numbering scheme is H2C1=CH22 for the olefin and Al-C-C-C for the growing chain.
Table S-II. Basis set influence (at the MP2 level) of olefin coordination and insertion; energies relative to complex [HC(NH)2Al CH2CH3(CH2CH2)]+ (kcal/mol).
EBSSE
Reactant 1a
(complexation)
TS 3
(Insertion)
Product 4
6-31G (d)
6.1
18.9
30.6
-9.0
6-31G (d,p)
6.0
18.6
30.2
-9.7
6-311G (d,p)
4.5
18.4
28.9
-11.2
6-311G (2d,p)
3.6
20.0
28.5
-10.0
Method
a
Corrected for BSSE.
2
Table S-III. Basis set influence (at the MP2 level) on the energies of -hydrogen transfer to the metal (BHE)
relative to precursor [HC(NH)2AlCH2CH3]+ (kcal/mol).
TS 7
(BHE)
Structure 8
Structure 9a
EBSSEb
Structure 10a
EBSSEc
6-31G (d)
39.2
14.1
9.9
5.2
36.9
5.8
6-31G (d,p)
39.8
15.5
10.9
5.1
38.1
5.7
6-311G (d,p)
38.7
16.2
11.2
4.1
38.1
4.1
6-311G (2d,p)
38.7
16.0
8.8
3.3
39.3
3.2
Method
a
Corrected for BSSE; b relative to 9; c relative to 8.
Table S-IV. Basis set influence (at the MP2 level)on the energies of different reactions relative to
[HC(NH)2AlCH2CH3(CH2CH2)]+ in kcal/mol.
E
TS 3
(Insertion)
TS 5
(BHT)
TS 6
(CHT)
TS 7a
(BHE)
6-31G (p)
30.6
24.7
54.1
58.1
5.9
6-31G (d,p)
30.2
23.0
52.0
58.4
7.2
6-311G (d,p)
28.9
21.4
49.1
57.1
7.5
6-311G (2d,p)
28.5
21.2
48.3
58.8
7.3
Method
a
chain growth-chain transfer
Corrected for BSSE.
3
Tables of cartesian coordinates optimized at MP2 level and the total energies computed at
CCSD(T) level of all species mentioned in the text.
Ethylene
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 C
2
2 C
1
1.334903( 1)
3
3 H
1
1.084765( 2)
2 121.704( 6)
4
4 H
1
1.084765( 3)
2 121.704( 7)
3 180.000( 10)
0
5
5 H
2
1.084765( 4)
1 121.704( 8)
3 180.000( 11)
0
6
6 H
2
1.084765( 5)
1 121.704( 9)
5 180.000( 12)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
6
0.000000
0.000000
0.667451
2
6
0.000000
0.000000
-0.667451
3
1
0.000000
0.922890
1.237530
4
1
0.000000
-0.922890
1.237530
5
1
0.000000
-0.922890
-1.237530
6
1
0.000000
0.922890
-1.237530
---------------------------------------------------------DD1Dir will call FoFMem
1 times, MxPair=
42
NAB=
21 NAA=
0 NBB=
0.
The Euclidean norm of the A-vectors is
0.3131148D-05
DE(CORR)= -0.28156041D+00
E(CORR)=
-0.78312630072D+02
NORM(A)=
0.10617637D+01
Dominant configurations:
***********************
Spin Case
I
J
A
B
Value
ABAB
8
8
9
9
-0.146796D+00
Largest amplitude= 1.47D-01
T4(AAA)= -0.16102092D-03
T4(AAB)= -0.47131497D-02
T5(AAA)= 0.12209276D-04
T5(AAB)= 0.23060927D-03
Time for triples=
16.96 seconds.
T4(CCSD)= -0.97483413D-02
T5(CCSD)= 0.48563708D-03
CCSD(T)= -0.78321892777D+02
4
Reactant 1
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 N
1
1.891674( 1)
3
3 H
2
1.013008( 2)
1 149.717( 14)
4
4 C
2
1.333918( 3)
3 121.463( 15)
1 179.358( 26)
0
5
5 H
4
1.090398( 4)
2 124.369( 16)
1 180.240( 27)
0
6
6 N
4
1.333545( 5)
2 111.243( 17)
3 -179.616( 28)
0
7
7 H
6
1.013044( 6)
4 121.543( 18)
2 180.161( 29)
0
8
8 C
1
1.928967( 7)
2 143.206( 19)
4 179.129( 30)
0
9
9 C
8
1.540758( 8)
1 114.093( 20)
2
-7.053( 31)
0
10 10 H
8
1.097322( 9)
9 110.571( 21)
1 121.658( 32)
0
11 11 H
8
1.097400( 10)
9 110.557( 22)
1 -121.889( 33)
0
12 12 H
9
1.092452( 11)
8 112.066( 23) 11 177.226( 34)
0
13 13 H
9
1.092423( 12)
8 112.058( 24) 10 -177.498( 35)
0
14 14 H
9
1.091995( 13)
8 109.686( 25) 13 119.138( 36)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
0.002342
-0.259330
-0.030184
2
7
1.231135
1.178874
-0.038359
3
1
1.411494
2.175191
-0.070077
4
6
2.226355
0.292739
0.021973
5
1
3.284101
0.556042
0.050522
6
7
1.760208
-0.956435
0.046732
7
1
2.383295
-1.753758
0.094661
8
6
-1.879162
-0.683686
-0.058124
9
6
-2.802591
0.543194
0.068293
10
1
-2.073454
-1.397632
0.752214
11
1
-2.088957
-1.229839
-0.986558
12
1
-2.647926
1.078169
1.008149
13
1
-2.659933
1.250301
-0.752094
14
1
-3.846079
0.222258
0.044106
---------------------------------------------------------DD1Dir will call FoFDir
1 times, MxPair=
272
NAB=
136 NAA=
0 NBB=
0.
Spin AB IR= 101 I=
9 J=
9 Mu=
42 Nu=
42 IOp=1 MuP=
42 NuP=
FactIJ= 0.0 Fact= 0.0 A=-3.5498618990D-01 AP=-3.5498618990D-01
The Euclidean norm of the A-vectors is
0.5444416D-05
DE(CORR)= -0.79899121D+00
E(CORR)=
-0.46970357664D+03
NORM(A)=
0.11463756D+01
Largest amplitude= 6.48D-02
T4(AAA)= -0.67798456D-03
T4(AAB)= -0.13157990D-01
T5(AAA)= 0.46312804D-04
T5(AAB)= 0.73750443D-03
Time for triples=
5294.96 seconds.
T4(CCSD)= -0.27671948D-01
T5(CCSD)= 0.15676345D-02
CCSD(T)= -0.46972968095D+03
42
5
-complex 2
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
1.934515( 1)
3
3 H
2
1.097569( 2)
1 109.748( 22)
4
4 H
2
1.097586( 3)
1 109.705( 23)
3 -115.453( 42)
0
5
5 C
2
1.541156( 4)
1 112.348( 24)
3 122.322( 43)
0
6
6 H
5
1.093321( 5)
2 111.786( 25)
4 177.321( 44)
0
7
7 H
5
1.093313( 6)
2 111.783( 26)
3 -177.068( 45)
0
8
8 H
5
1.092621( 7)
2 110.662( 27)
7 119.503( 46)
0
9
9 N
1
1.914328( 8)
2 132.140( 28)
4
72.535( 47)
0
10 10 C
9
1.331874( 9)
1
89.188( 29)
2 127.943( 48)
0
11 11 N
10
1.332112( 10)
1
55.697( 30)
9 -176.611( 49)
0
12 12 H
9
1.012748( 11)
1 149.778( 31) 10 -170.264( 50)
0
13 13 H
10
1.091092( 12)
9 124.356( 32)
1 -177.173( 51)
0
14 14 H
11
1.012731( 13) 10 120.592( 33)
9 -177.578( 52)
0
15
X
1
2.356851( 14)
2 109.037( 34)
5 -178.496( 53)
0
16 15 C
15
0.676532( 15)
1
90.005( 35)
2 -89.033( 54)
0
17
X
15
1.000000( 16) 16
90.000( 36)
1
0.000( 55)
0
18 16 C
15
0.676532( 17) 17
90.000( 37) 16 180.000( 56)
0
19 17 H
16
1.085671( 18) 18 121.224( 38)
1 -98.071( 57)
0
20 18 H
16
1.088460( 19) 18 121.272( 39) 19 -174.282( 58)
0
21 19 H
18
1.088516( 20) 16 121.266( 40) 19 174.351( 59)
0
22 20 H
18
1.085621( 21) 19
95.379( 41) 21 -171.010( 60)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
0.095074
-0.077423
-0.007604
2
6
1.839091
-0.914495
-0.015470
3
1
1.938406
-1.556312
-0.900267
4
1
1.930321
-1.587784
0.846536
5
6
2.984146
0.116718
0.009228
6
1
2.954201
0.777255
-0.861487
7
1
2.947774
0.742007
0.905344
8
1
3.954844
-0.384803
0.002736
9
7
-0.670441
1.285601
1.097297
10
6
-1.012538
1.957135
-0.000839
11
7
-0.694162
1.279335
-1.102541
12
1
-0.812768
1.691462
2.014181
13
1
-1.494749
2.935884
0.001106
14
1
-0.859439
1.677958
-2.018733
15
6
-1.558473
-1.764619
-0.664759
16
6
-1.565430
-1.742026
0.688098
17
1
-2.300879
-1.220574
-1.240545
18
1
-0.867714
-2.400285
-1.215692
19
1
-0.879655
-2.358069
1.266951
20
1
-2.314859
-1.181070
1.237878
---------------------------------------------------------DD1Dir will call FoFDir
1 times, MxPair=
506
NAB=
253 NAA=
0 NBB=
0.
Spin AB IR= 199 I= 13 J= 13 Mu=
80 Nu=
80 IOp=1 MuP=
80 NuP=
FactIJ= 0.0 Fact= 0.0 A=-4.6532834924D-01 AP=-4.6532834924D-01
The Euclidean norm of the A-vectors is
0.7995369D-05
DE(CORR)= -0.10873041D+01
E(CORR)=
-0.54805067865D+03
NORM(A)=
0.11990484D+01
Largest amplitude= 6.75D-02
T4(AAA)= -0.93831506D-03
T4(AAB)= -0.18510157D-01
T5(AAA)= 0.59723962D-04
T5(AAB)= 0.94510047D-03
Time for triples=
39574.64 seconds.
T4(CCSD)= -0.38896945D-01
T5(CCSD)= 0.20096489D-02
CCSD(T)= -0.54808756595D+03
80
6
TS 3 (insertion)
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
2.295057( 1)
3
3 N
2
1.333225( 2)
1
55.640( 20)
4
4 N
2
1.331391( 3)
3 111.618( 21)
1
-1.950( 38)
0
5
5 H
2
1.090439( 4)
3 124.105( 22)
4 180.149( 39)
0
6
6 H
3
1.012121( 5)
2 120.827( 23)
4 181.440( 40)
0
7
7 H
4
1.012346( 6)
2 120.743( 24)
3 -181.461( 41)
0
8
8 C
1
2.061399( 7)
3 111.386( 25)
2 112.566( 42)
0
9
9 C
8
1.530122( 8)
1 109.951( 26)
6
34.848( 43)
0
10 10 H
8
1.109545( 9)
9 111.160( 27)
1
90.189( 44)
0
11 11 H
8
1.088880( 10)
9 111.527( 28)
1 -155.107( 45)
0
12 12 H
9
1.093268( 11)
8 111.558( 29) 10 181.859( 46)
0
13 13 H
9
1.093052( 12)
8 112.710( 30) 12 -121.648( 47)
0
14 14 H
9
1.093612( 13)
8 109.982( 31) 12 118.790( 48)
0
15 15 C
1
2.204499( 14)
8
62.385( 32) 10 147.492( 49)
0
16 16 C
15
1.438190( 15)
1
61.865( 33)
8 169.981( 50)
0
17 17 H
15
1.087248( 16) 16 118.883( 34)
1 -101.005( 51)
0
18 18 H
15
1.085696( 17) 16 120.640( 35)
1 108.031( 52)
0
19 19 H
16
1.088578( 18) 15 116.316( 36) 18 -142.971( 53)
0
20 20 H
16
1.088778( 19) 15 116.475( 37) 17 148.779( 54)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
-0.207037
0.344970
-0.020178
2
6
-2.394577
-0.349258
-0.022028
3
7
-1.497352
-0.686413
-0.948744
4
7
-1.854808
0.408108
0.930678
5
1
-3.440036
-0.658562
-0.042070
6
1
-1.763955
-1.244207
-1.750103
7
1
-2.419495
0.761232
1.693093
8
6
1.261648
-0.847931
0.797940
9
6
1.723308
-1.885233
-0.227802
10
1
0.419818
-1.235245
1.408186
11
1
2.034886
-0.645658
1.537433
12
1
2.574082
-1.522620
-0.810838
13
1
0.932148
-2.168721
-0.926704
14
1
2.046387
-2.797071
0.282255
15
6
1.827839
1.181163
0.120801
16
6
0.847391
1.907507
-0.640472
17
1
2.062833
1.514764
1.128569
18
1
2.637071
0.655942
-0.377217
19
1
0.491239
2.839227
-0.204518
20
1
0.987965
1.926943
-1.719962
---------------------------------------------------------DE(CORR)= -0.10956877D+01
E(CORR)=
NORM(A)=
0.12017481D+01
Largest amplitude= 5.13D-02
T4(AAA)= -0.10651453D-02
T4(AAB)= -0.19739589D-01
T5(AAA)= 0.68748974D-04
T5(AAB)= 0.11336342D-02
Time for triples=
31871.47 seconds.
T4(CCSD)= -0.41609469D-01
T5(CCSD)= 0.24047663D-02
CCSD(T)= -0.54803741168D+03
-0.54799820698D+03
7
Product 4
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 N
1
1.895702( 1)
3
3 H
2
1.012714( 2)
1 149.667( 20)
4
4 C
2
1.333397( 3)
3 121.343( 21)
1 182.582( 38)
0
5
5 H
4
1.090527( 4)
2 124.314( 22)
1 181.091( 39)
0
6
6 N
4
1.332456( 5)
2 111.320( 23)
3 -180.221( 40)
0
7
7 H
6
1.012763( 6)
4 121.241( 24)
2 180.999( 41)
0
8
8 C
1
1.929450( 7)
2 145.499( 25)
4 -188.688( 42)
0
9
9 C
8
1.543353( 8)
1 101.225( 26)
2 115.795( 43)
0
10 10 H
8
1.096526( 9)
9 110.863( 27)
1 116.273( 44)
0
11 11 H
8
1.093646( 10)
9 112.944( 28)
1 -123.624( 45)
0
12 12 H
9
1.095784( 11)
8 110.214( 29) 11 -38.435( 46)
0
13 13 H
9
1.094680( 12)
8 110.953( 30) 10 -40.610( 47)
0
14 14 C
9
1.528807( 13)
8 110.504( 31) 13 121.357( 48)
0
15 15 H
14
1.124525( 14)
9 109.295( 32) 13 -178.534( 49)
0
16 16 H
14
1.098727( 15)
9 109.726( 33) 12 181.190( 50)
0
17 17 C
14
1.523621( 16)
9 114.956( 34) 15 118.929( 51)
0
18 18 H
17
1.092587( 17) 14 109.529( 35) 15 -177.520( 52)
0
19 19 H
17
1.091710( 18) 14 111.549( 36) 18 119.589( 53)
0
20 20 H
17
1.092283( 19) 14 110.849( 37) 18 -119.342( 54)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
0.725852
0.577823
-0.033618
2
7
2.089184
-0.250857
-1.057483
3
1
2.519920
-0.431565
-1.956038
4
6
2.616884
-0.723385
0.072207
5
1
3.524015
-1.326631
0.121762
6
7
1.893878
-0.363845
1.132127
7
1
2.168293
-0.630085
2.069944
8
6
-0.766593
1.800247
-0.066208
9
6
-1.935186
0.857240
0.290260
10
1
-0.887831
2.207480
-1.077065
11
1
-0.683478
2.652277
0.614379
12
1
-2.024729
0.759736
1.378018
13
1
-2.887397
1.261033
-0.068306
14
6
-1.712145
-0.526433
-0.320439
15
1
-0.747131
-0.953090
0.068490
16
1
-1.599730
-0.437281
-1.409758
17
6
-2.786886
-1.555119
0.008436
18
1
-3.748442
-1.217391
-0.385386
19
1
-2.561498
-2.526538
-0.435835
20
1
-2.885944
-1.682028
1.088790
---------------------------------------------------------DE(CORR)= -0.10887892D+01
E(CORR)=
NORM(A)=
0.11940110D+01
Largest amplitude= 4.94D-02
T4(AAA)= -0.97112351D-03
T4(AAB)= -0.17978105D-01
T5(AAA)= 0.57810712D-04
T5(AAB)= 0.89721687D-03
Time for triples=
40030.42 seconds.
T4(CCSD)= -0.37898457D-01
T5(CCSD)= 0.19100552D-02
CCSD(T)= -0.54809954261D+03
-0.54806355421D+03
8
TS 5 (BHT)
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
2.325295( 1)
3
3 N
2
1.330950( 2)
1
55.816( 20)
4
4 N
2
1.330971( 3)
3 111.628( 21)
1
0.003( 38)
0
5
5 H
2
1.091224( 4)
3 124.186( 22)
4 -179.999( 39)
0
6
6 H
3
1.011984( 5)
2 120.196( 23)
4 180.000( 40)
0
7
7 H
4
1.011985( 6)
2 120.197( 24)
3 -179.993( 41)
0
8
8 C
1
2.036598( 7)
2 128.333( 25)
3
89.977( 42)
0
9
9 C
8
1.442251( 8)
1 115.784( 26)
4 138.301( 43)
0
10 10 H
8
1.093762( 9)
9 113.286( 27)
1 -116.091( 44)
0
11 11 H
8
1.093798( 10)
9 113.281( 28) 10 -127.827( 45)
0
12 12 H
9
1.090867( 11)
8 118.000( 29) 11 -134.701( 46)
0
13 13 H
9
1.090902( 12)
8 117.993( 30) 10 134.790( 47)
0
14 14 H
9
1.291127( 13)
8 108.434( 31) 11 116.132( 48)
0
15 15 C
1
2.036608( 14)
4 120.565( 32)
7
65.631( 49)
0
16 16 C
15
1.442206( 15) 14
33.499( 33)
1 -180.095( 50)
0
17 17 H
15
1.093715( 16) 16 113.288( 34) 14 -116.004( 51)
0
18 18 H
15
1.093772( 17) 16 113.281( 35) 17 -127.830( 52)
0
19 19 H
16
1.090847( 18) 15 118.002( 36) 18 -134.669( 53)
0
20 20 H
16
1.090868( 19) 15 117.987( 37) 17 134.820( 54)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
-0.336740
-0.000024
-0.000124
2
6
-2.662035
0.000011
0.000093
3
7
-1.914127
0.000033
1.101030
4
7
-1.914268
-0.000093
-1.100965
5
1
-3.753259
0.000089
0.000155
6
1
-2.351627
0.000114
2.013558
7
1
-2.351876
-0.000008
-2.013440
8
6
0.926403
-1.597585
0.000447
9
6
2.334204
-1.284241
-0.000530
10
1
0.600805
-2.122131
0.903305
11
1
0.599927
-2.123396
-0.901401
12
1
2.903459
-1.481723
0.908832
13
1
2.902078
-1.481656
-0.910813
14
1
2.466597
0.000080
-0.000521
15
6
0.926364
1.597581
-0.000553
16
6
2.334129
1.284289
0.000620
17
1
0.600925
2.122353
-0.903280
18
1
0.599677
2.123059
0.901382
19
1
2.903696
1.482581
-0.908348
20
1
2.901585
1.481035
0.911266
---------------------------------------------------------DE(CORR)= -0.10975322D+01
E(CORR)=
NORM(A)=
0.12063145D+01
Largest amplitude= 7.92D-02
T4(AAA)= -0.11447073D-02
T4(AAB)= -0.20291923D-01
T5(AAA)= 0.60916811D-04
T5(AAB)= 0.12846929D-02
Time for triples=
30544.22 seconds.
T4(CCSD)= -0.42873260D-01
T5(CCSD)= 0.26912194D-02
CCSD(T)= -0.54804701675D+03
-0.54800683470D+03
9
TS 6 (CHT)
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
2.289492( 1)
3
3 N
2
1.333169( 2)
1
55.734( 20)
4
4 N
2
1.332019( 3)
3 111.557( 21)
1
1.403( 38)
0
5
5 H
2
1.090245( 4)
3 124.195( 22)
4 -180.029( 39)
0
6
6 H
3
1.012233( 5)
2 121.032( 23)
4 179.393( 40)
0
7
7 H
4
1.012343( 6)
2 121.062( 24)
3 -179.168( 41)
0
8
8 C
1
2.055119( 7)
2 131.609( 25)
3
86.285( 42)
0
9
9 C
8
1.540563( 8)
1 108.381( 26)
3 -29.017( 43)
0
10 10 H
8
1.099746( 9)
1 128.409( 27)
4 109.636( 44)
0
11 11 H
8
1.102800( 10)
9 112.024( 28) 10 112.611( 45)
0
12 12 H
9
1.093485( 11)
8 111.284( 29) 11 -180.668( 46)
0
13 13 H
9
1.092749( 12)
8 112.147( 30) 12 121.033( 47)
0
14 14 H
9
1.092367( 13)
8 110.539( 31) 13 119.925( 48)
0
15 15 C
1
2.014515( 14)
4 123.930( 32)
2 -123.754( 49)
0
16 16 C
15
1.356055( 15)
1 119.881( 33)
4 142.832( 50)
0
17 17 H
15
1.090591( 16) 16 117.859( 34)
1 163.030( 51)
0
18 18 H
16
1.089955( 17) 15 121.890( 35) 17 183.760( 52)
0
19 19 H
16
1.088000( 18) 15 122.907( 36) 18 179.055( 53)
0
20 20 H
1
1.675007( 19)
4 140.694( 37)
2 177.469( 54)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
0.214580
-0.167061
-0.231476
2
6
2.432054
-0.058787
0.327860
3
7
1.431217
0.162063
1.180438
4
7
1.981824
-0.321037
-0.898024
5
1
3.487228
-0.027967
0.600428
6
1
1.611636
0.366379
2.155281
7
1
2.620601
-0.523150
-1.656940
8
6
-1.112951
1.281086
-0.834837
9
6
-1.438116
2.176772
0.375680
10
1
-2.019459
1.164841
-1.446534
11
1
-0.414878
1.769545
-1.535031
12
1
-2.139783
1.685803
1.055623
13
1
-0.543788
2.438757
0.946331
14
1
-1.903457
3.109312
0.048432
15
6
-1.176959
-1.615132
-0.389525
16
6
-2.050317
-1.826574
0.626066
17
1
-1.063454
-2.401896
-1.136189
18
1
-2.259935
-1.061817
1.373868
19
1
-2.601345
-2.756787
0.747788
20
1
-1.376453
-0.222599
-0.752223
---------------------------------------------------------DE(CORR)= -0.10999708D+01
E(CORR)=
NORM(A)=
0.12042885D+01
Largest amplitude= 7.31D-02
T4(AAA)= -0.10315790D-02
T4(AAB)= -0.19988196D-01
T5(AAA)= 0.63055603D-04
T5(AAB)= 0.10399748D-02
Time for triples=
40486.87 seconds.
T4(CCSD)= -0.42039549D-01
T5(CCSD)= 0.22060608D-02
CCSD(T)= -0.54799913447D+03
-0.54795930098D+03
10
TS 7 (BHE)
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
2.280567( 1)
3
3 N
2
1.332497( 2)
1
55.846( 14)
4
4 N
2
1.332448( 3)
3 111.705( 15)
1
-0.739( 26)
0
5
5 H
2
1.090007( 4)
3 124.146( 16)
4 -179.961( 27)
0
6
6 H
3
1.012236( 5)
2 121.303( 17)
4 180.566( 28)
0
7
7 H
4
1.012172( 6)
2 121.357( 18)
3 -180.382( 29)
0
8
8 C
1
2.020224( 7)
2 141.541( 19)
4
89.840( 30)
0
9
9 C
8
1.421860( 8)
1
78.802( 20)
4 -131.187( 31)
0
10 10 H
8
1.087993( 9)
9 117.084( 21)
1 -108.026( 32)
0
11 11 H
8
1.088346( 10)
9 117.091( 22) 10 -144.102( 33)
0
12 12 H
9
1.087381( 11)
8 121.129( 23) 10 151.087( 34)
0
13 13 H
9
1.087419( 12)
8 121.105( 24) 11 -151.167( 35)
0
14 14 H
1
1.655026( 13)
3 121.442( 25)
6
62.068( 36)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
-0.165616
-0.002285
-0.193289
2
6
2.098828
0.001909
0.077382
3
7
1.353090
1.103193
-0.003832
4
7
1.357427
-1.102296
-0.003081
5
1
3.182382
0.004091
0.195794
6
1
1.770273
2.024733
0.032813
7
1
1.777048
-2.022521
0.036858
8
6
-1.885507
0.000517
0.866554
9
6
-2.382172
0.000233
-0.465741
10
1
-1.994477
-0.920104
1.436038
11
1
-1.989868
0.923207
1.434225
12
1
-2.742139
0.914413
-0.931676
13
1
-2.745412
-0.913722
-0.929663
14
1
-1.065313
-0.002631
-1.582409
---------------------------------------------------------DD1Dir will call FoFDir
1 times, MxPair=
272
NAB=
136 NAA=
0 NBB=
0.
Spin AB IR= 116 I= 11 J= 11 Mu=
25 Nu=
25 IOp=1 MuP=
25 NuP=
FactIJ= 0.0 Fact= 0.0 A=-5.8784089079D-01 AP=-5.8784089079D-01
The Euclidean norm of the A-vectors is
0.7921390D-05
DE(CORR)= -0.80144047D+00
E(CORR)=
-0.46964188144D+03
NORM(A)=
0.11528126D+01
Largest amplitude= 4.77D-02
T4(AAA)= -0.76629002D-03
T4(AAB)= -0.14404643D-01
T5(AAA)= 0.54027398D-04
T5(AAB)= 0.92636733D-03
Time for triples=
5133.25 seconds.
T4(CCSD)= -0.30341866D-01
T5(CCSD)= 0.19607895D-02
CCSD(T)= -0.46967026252D+03
25
11
Structure 8
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
2.306458( 1)
3
3 N
2
1.332523( 2)
1
55.656( 16)
4
4 N
2
1.332393( 3)
3 111.254( 17)
1
-2.973( 30)
0
5
5 H
2
1.090741( 4)
3 124.357( 18)
4 180.106( 31)
0
6
6 H
3
1.012754( 5)
2 120.861( 19)
4 182.620( 32)
0
7
7 H
4
1.012765( 6)
2 120.864( 20)
3 -182.674( 33)
0
8
8 H
1
1.559433( 7)
2 144.998( 21)
3
91.890( 34)
0
9
X
1
2.322742( 8)
8 105.607( 22)
3 128.321( 35)
0
10
9 C
9
0.677134( 9)
1
90.101( 23)
8 -89.294( 36)
0
11
X
9
1.000000( 10) 10
90.000( 24)
1
0.000( 37)
0
12 10 C
9
0.677134( 11) 11
90.000( 25) 10 180.000( 38)
0
13 11 H
10
1.085885( 12) 12 121.199( 26)
1 -99.082( 39)
0
14 12 H
10
1.089198( 13) 12 121.249( 27) 13 -174.186( 40)
0
15 13 H
12
1.089290( 14) 10 121.241( 28) 13 174.140( 41)
0
16 14 H
12
1.085835( 15) 10 121.211( 29) 15 -174.039( 42)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
-0.054830
-0.005857
0.854284
2
6
1.799969
0.001565
-0.516634
3
7
1.175337
-1.100394
-0.102941
4
7
1.177494
1.099129
-0.088674
5
1
2.703135
0.004380
-1.128188
6
1
1.547741
-2.018494
-0.312890
7
1
1.552045
2.019176
-0.285949
8
1
-0.550385
-0.011841
2.332871
9
6
-1.984684
-0.672037
-0.446127
10
6
-1.970101
0.682140
-0.452036
11
1
-1.597479
-1.242410
-1.285111
12
1
-2.468448
-1.228395
0.355616
13
1
-2.442414
1.255687
0.344529
14
1
-1.572337
1.236885
-1.296477
---------------------------------------------------------DD1Dir will call FoFDir
1 times, MxPair=
272
NAB=
136 NAA=
0 NBB=
0.
Spin AB IR= 116 I= 11 J= 11 Mu=
25 Nu=
25 IOp=1 MuP=
25 NuP=
FactIJ= 0.0 Fact= 0.0 A=-4.4940089897D-01 AP=-4.4940089897D-01
The Euclidean norm of the A-vectors is
0.4715827D-05
DE(CORR)= -0.79894981D+00
E(CORR)=
-0.46968210595D+03
NORM(A)=
0.11513837D+01
Largest amplitude= 5.49D-02
T4(AAA)= -0.71205693D-03
T4(AAB)= -0.14028945D-01
T5(AAA)= 0.49145168D-04
T5(AAB)= 0.77126737D-03
Time for triples=
5105.30 seconds.
T4(CCSD)= -0.29482004D-01
T5(CCSD)= 0.16408251D-02
CCSD(T)= -0.46970994713D+03
25
12
Structure 9
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
2.318399( 1)
3
3 N
2
1.331648( 2)
1
55.576( 24)
4
4 N
2
1.331678( 3)
3 111.155( 25)
1
-0.009( 46)
0
5
5 H
2
1.090815( 4)
3 124.413( 26)
4 180.001( 47)
0
6
6 H
3
1.012840( 5)
2 120.854( 27)
4 180.005( 48)
0
7
7 H
4
1.012850( 6)
2 120.837( 28)
3 -180.003( 49)
0
8
8 H
1
1.560808( 7)
2 179.952( 29)
3 -188.226( 50)
0
9
X
1
2.551389( 8)
8
88.104( 30)
3
89.957( 51)
0
10
9 C
9
0.674040( 9)
1
89.981( 31)
8 -89.992( 52)
0
11
X
9
1.000000( 10) 10
90.000( 32)
1
0.000( 53)
0
12 10 C
9
0.674040( 11) 11
90.000( 33) 10 180.000( 54)
0
13 11 H
10
1.084237( 12) 12 121.278( 34)
1 -104.131( 55)
0
14 12 H
10
1.087232( 13) 12 121.444( 35) 13 -174.058( 56)
0
15 13 H
12
1.087227( 14) 10 121.451( 36) 13 174.087( 57)
0
16 14 H
12
1.084240( 15) 10 121.279( 37) 15 -174.179( 58)
0
17
X
1
2.551031( 16)
8
88.093( 38)
3 -89.954( 59)
0
18 15 C
17
0.674043( 17)
1
89.973( 39)
8
89.984( 60)
0
19
X
17
1.000000( 18) 18
90.000( 40)
1
0.000( 61)
0
20 16 C
17
0.674043( 19) 19
90.000( 41) 18 180.000( 62)
0
21 17 H
18
1.084237( 20) 20 121.277( 42)
1 104.183( 63)
0
22 18 H
18
1.087236( 21) 20 121.443( 43) 21 174.031( 64)
0
23 19 H
20
1.084244( 22) 18 121.278( 44) 22 174.108( 65)
0
24 20 H
20
1.087228( 23) 18 121.452( 45) 23 -174.159( 66)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
-0.000050
-0.563158
-0.002092
2
6
-0.000201
1.755236
0.002946
3
7
0.000032
1.000046
1.099747
4
7
-0.000138
1.004870
-1.097199
5
1
-0.000404
2.846048
0.005536
6
1
-0.000060
1.421631
2.020677
7
1
-0.000346
1.430778
-2.016148
8
1
-0.000136
-2.123960
-0.006780
9
6
2.549199
-0.649817
0.673632
10
6
2.550676
-0.645585
-0.674441
11
1
2.804459
0.239039
1.239624
12
1
2.386109
-1.564824
1.237757
13
1
2.388390
-1.556875
-1.244769
14
1
2.805738
0.247205
-1.234304
15
6
-2.548806
-0.650102
0.673727
16
6
-2.550539
-0.645701
-0.674351
17
1
-2.804843
0.238435
1.239869
18
1
-2.385130
-1.565104
1.237698
19
1
-2.806831
0.246847
-1.234044
20
1
-2.387531
-1.556765
-1.244839
---------------------------------------------------------DE(CORR)= -0.10892501D+01
E(CORR)=
NORM(A)=
0.12058560D+01
Largest amplitude= 6.09D-02
T4(AAA)= -0.96958325D-03
T4(AAB)= -0.19599966D-01
T5(AAA)= 0.62690319D-04
T5(AAB)= 0.10007197D-02
Time for triples=
31954.60 seconds.
T4(CCSD)= -0.41139099D-01
T5(CCSD)= 0.21268201D-02
CCSD(T)= -0.54804372746D+03
-0.54800471518D+03
13
Structure 10
-----------------------------------------------------------------------Z-MATRIX (ANGSTROMS AND DEGREES)
CD Cent Atom N1
Length/X
N2
Alpha/Y
N3
Beta/Z
J
-----------------------------------------------------------------------1
1 Al
2
2 C
1
2.279010( 1)
3
3 N
2
1.334747( 2)
1
55.565( 8)
4
4 N
2
1.335142( 3)
3 111.110( 9)
1
-0.010( 14)
0
5
5 H
2
1.090040( 4)
3 124.453( 10)
4 179.995( 15)
0
6
6 H
3
1.013450( 5)
2 121.872( 11)
4 179.956( 16)
0
7
7 H
4
1.013430( 6)
2 121.875( 12)
3 -180.062( 17)
0
8
8 H
1
1.552160( 7)
3 143.960( 13)
2 180.006( 18)
0
-----------------------------------------------------------------------Standard orientation:
---------------------------------------------------------Center
Atomic
Coordinates (Angstroms)
Number
Number
X
Y
Z
---------------------------------------------------------1
13
1.099682
-0.000794
0.000021
2
6
-1.179328
0.000605
0.000033
3
7
-0.423887
1.100995
0.000065
4
7
-0.424645
-1.100785
-0.000219
5
1
-2.269368
0.000926
0.000263
6
1
-0.830552
2.029275
-0.000416
7
1
-0.832089
-2.028702
0.000660
8
1
2.651835
0.003724
0.000106
---------------------------------------------------------DD1Dir will call FoFMem
1 times, MxPair=
110
NAB=
55 NAA=
0 NBB=
0.
The Euclidean norm of the A-vectors is
0.4974486D-05
DE(CORR)= -0.51164566D+00
E(CORR)=
-0.39132909977D+03
NORM(A)=
0.10964382D+01
Largest amplitude= 6.60D-02
T4(AAA)= -0.46563710D-03
T4(AAB)= -0.87034305D-02
T5(AAA)= 0.35542099D-04
T5(AAB)= 0.55224452D-03
Time for triples=
301.27 seconds.
T4(CCSD)= -0.18338135D-01
T5(CCSD)= 0.11755732D-02
CCSD(T)= -0.39134626234D+03
14