Supporting Information
1. 4-nitroimidazole potential energy surfaces
Figure 1A. Potential energy surfaces from (S1/S0)CI for 4-nitroimidazole. One path goes down to
nitro-nitrite isomer, the other one goes back to Frank Condon geometry.
1
Figure 1B. Potential energy surfaces continue the path which goes back to Frank Condon
geometry shown in Figure 1A for 4-nitroimidazole.
2
Figure 1C. Locating the (S2/S1)CI from the Frank Condon geometry for 4-nitroimidazole.
3
2. 2-nitroimidazole potential energy surfaces
Figure 2A. Potential energy surfaces from (S1/S0)CI for 2-nitroimidazole. One path goes down to
nitro-nitrite isomer, the other one goes back to Frank Condon geometry.
4
Figure 2B. Potential energy surfaces continue the path which goes back to Frank Condon
geometry shown in Figure 2A for 2-nitroimidazole.
5
Figure 2C. Locating the (S2/S1)CI from the Frank Condon geometry for 2-nitroimidazole.
6
3. 1-methyl-5-nitroimidazole potential energy surfaces
Figure 3A. Potential energy surfaces from (S1/S0)CI for 1-methyl-5-nitroimidazole. One path goes
down to nitro-nitrite isomer, the other one goes back to Frank Condon geometry.
7
Figure 3B. Potential energy surfaces continue the path which goes back to Frank Condon
geometry shown in Figure 3A for 1-methyl-5-nitroimidazole.
8
Figure 3C. Locating the (S2/S1)CI from the minimum structure of 1-methyl-5-nitroimidazole on S2.
9
4. Searching Conical Intersection
Since the conical intersections are key features for the excited electronic state processes of
nitroimidazole molecules, steps to locate the conical intersections are described simply here.
1) Predict a starting geometry for the conical intersection. This could be a relevant transition
state structure, FC geometry, another isomeric minimum, etc.
2) Compute and examine the canonical orbitals at the RHF/STO-3G level in order to select the
proper active space for a CASSCF calculation.
Take 4-nitroimidazole as an example. Firstly, find a transition state of nitro-nitrite isomer for
4-nitroimidazole using MP2/6-31G(d) base set. Secondly, change the structure a little to make it
close to the final structure of the conical intersection (or just start from the transition state
structure). Thirdly, run HF/sto-3g job to select the proper orbitals.
Input file is given below:
%chk=pop.chk
%mem=4000MB
%nprocshared=4
#p HF/sto-3g gfinput pop=full scf=maxcycle=1000
population analysis to choose proper orbitals
01
N
C
N
C
C
H
H
H
N
O
O
-2.55662389
-2.50833089
-1.26195189
-0.48485389
-1.24431889
-3.38702789
-3.39666289
-0.99294789
1.95078289
2.55886689
2.48868889
0.67622425
-0.71074875
-1.15501775
0.04237025
1.13613025
1.25066125
-1.32682975
2.18489525
-0.09699325
1.10353775
-1.17196025
-0.22517395
-0.11326395
0.07600205
0.06960705
-0.10510595
-0.36951695
-0.16795895
-0.15576095
0.50801895
0.01488595
-0.26330505
3) Perform a CAS/STO-3G calculation on the ground state, using the active space selected at a
RHF/STO-3G level. Recheck the CAS orbitals in the active space to make sure that the chosen
10
orbitals actually are in the active space. Run a series of CAS calculations on the ground state,
using the sequence of basis sets: STO-3G, 4-31G, and 6-31G(d).
4) Perform a state averaged CAS/6-31G(d) calculation for the excited state of interest (as
specified by the NRoot option). For this state averaged CAS the weight for each state should be
specified in a separate input section. As a conical intersection is an intersection between two
surfaces, a state averaged CAS is necessary because only state averaged CAS orbitals provide
the best description of the specified group of states as a whole. Rule of thumb is to use equal
weights (0.5 and 0.5) for the two states between which conical intersection is predicted to be
present.
5) Once the state averaged CAS job has completed, characterize the states and compare their
energies. Generally, it is found from experience that if a considerably large energy difference (>1
eV) between excited states is found, the starting geometry is not good enough to locate a conical
intersection (you may not get a converged result after hundreds of cycles). It is necessary to
predict another starting geometry.
6) Locate the conical intersection by running a CAS job with Opt=Conical option. To begin with
small base set like STO-3G
Input file is given below:
%chk=S1S0CIf.chk
%mem=4000MB
%nprocshared=4
#p opt=(conical,loose,maxcycle=100) CASSCF(10,7,nroot=2)/sto-3g guess=read geom=check scf=(maxcycle=2000)
pop=full gfinput nosymm
Search conical intersection (S1/S0)CI
01
Note: It is important to use “Guess=read Geom=Check” keyword, in order to make sure the right orbitals
are chosen.
11
And then increase the base set to 4-31G, 6-31G(d) by reading orbitals from STO-3G base set.
Input file is given below:
%chk= S1S0CIfffft.chk
%mem=4000MB
%nprocshared=4
#p opt=(conical, maxcycle=100, tight) CASSCF(10, 7, nroot=2)/6-31g(d) guess=read geom=check
scf=(maxcycle=2000) pop=full gfinput nosymm
read from orbitals from 4-31G base set
01
…
Final Output file as below:
……
……
……
State Average Calculation.
The weights are:
St.: 1 w.=0.500000 # St.: 2 w.=0.500000 # St.:
2ND ORD PT ENERGY
CV
0.000000
CU
0.000000
UV
0.000000
TOTAL
-428.210451
ITN= 1 MaxIt=*** E=
-428.2104506390 DE=-4.28D+02 Acc= 1.00D-08 Lan=
ITN= 2 MaxIt=*** E=
-428.2104506895 DE=-5.05D-08 Acc= 1.00D-08 Lan=
ITN= 3 MaxIt=*** E=
-428.2104507118 DE=-2.24D-08 Acc= 1.00D-08 Lan=
ITN= 4 MaxIt=*** E=
-428.2104507201 DE=-8.23D-09 Acc= 1.00D-08 Lan=
... Do an extra-iteration for final printing.
EIGENVALUES AND
0
0
0
0
EIGENVECTORS OF CI MATRIX
( 1)
EIGENVALUE
-428.2104511725
(
1) 0.7954544 (
4) 0.3391071 (
10)-0.2974243
(
56)-0.1165580 (
6)-0.0820281
(
40)-0.0786776 (
18) 0.0704158 (
58)-0.0632992
0.0613907 ( 139) 0.0603019
(
16)-0.0589056 (
12)-0.0482842 (
29)-0.0446098
(
26)-0.0321503 (
21) 0.0317962
(
8)-0.0304578 (
43)-0.0279412 ( 141)-0.0268033
0.0232743 (
47) 0.0227705
(
46)-0.0227642 (
78) 0.0225935 (
76)-0.0210763
0.0188755 (
35) 0.0182005
( 102)-0.0166303 (
93)-0.0165083 (
91)-0.0163420
0.0155198 (
7)-0.0155000
( 127)-0.0150636 ( 124)-0.0150555 (
15)-0.0145869
(
33)-0.0125347 (
99) 0.0117194
(
20) 0.0115973 (
( 2)
EIGENVALUE
-428.2104507224
(
2) 0.8353251 (
6)-0.3062005 (
1)-0.2423548
(
45)-0.1136056 (
36) 0.1095558
(
76)-0.0958020 (
4)-0.0816839 (
21) 0.0770425
(
55)-0.0655872 (
16)-0.0579202
(
70) 0.0578121 (
28) 0.0572628 (
18)-0.0502818
0.0426985 (
11) 0.0365820
(
93)-0.0343521 (
20) 0.0343317 ( 119) 0.0336119
(
61)-0.0300827 (
78) 0.0282706
(
38)-0.0279611 ( 135)-0.0268589 ( 103)-0.0265163
0.0244241 (
23)-0.0244156
12
(
2) 0.2400544 (
28)-0.1702939
(
98)-0.0632040 (
38) 0.0631026 (
(
45)-0.0368915 (
13)-0.0365021
(
70) 0.0260405 (
55)-0.0247563 (
36)
(
41)-0.0210002 (
9) 0.0202584 (
88)
(
64)-0.0158464 (
63) 0.0156088 (
51)
(
83)-0.0140366 (
100)-0.0131183
(
69) 0.1542475 (
58)-0.1372714
(
141)-0.0757432 (
10) 0.0732855
(
100)-0.0489798 (
102)-0.0444585 (
(
59)-0.0334838 (
9)-0.0333147
(
12) 0.0260108 (
73)-0.0253371 (
69)
56)
167)
(
25) 0.0243215 ( 109) 0.0235881 (
44)-0.0234372 (
30) 0.0231951 (
40) 0.0227707
( 153)-0.0221446 (
57)-0.0220505
( 112)-0.0217984 ( 139)-0.0207832 ( 124)-0.0200178 (
29) 0.0194637 (
98) 0.0187920
(
39)-0.0185809 (
66) 0.0183215
( 138) 0.0178533 (
Final one electron symbolic density matrix:
1
2
3
4
5
1 0.192782D+01
2 -0.772156D-03 0.198388D+01
3 0.354229D-01 -0.120218D-01 0.194084D+01
4 0.255449D-02 0.159687D-01 0.536962D-02 0.177132D+01
5 0.279070D-01 0.435055D-02 0.940299D-02 -0.221956D+00 0.116535D+01
6 0.101406D-01 0.178783D-02 0.705885D-01 0.453979D+00 -0.492119D+00
7 -0.961605D-01 0.872465D-02 0.555307D-01 0.404565D-01 -0.394084D-01
6
7
6 0.102685D+01
7 -0.472478D-02 0.183933D+00
Density Matrix for State
1
1
2
3
4
5
1 0.198608D+01
2 0.772319D-03 0.199592D+01
3 -0.354226D-01 0.120218D-01 0.190241D+01
4 -0.255410D-02 -0.159686D-01 -0.536959D-02 0.161823D+01
5 -0.279089D-01 -0.435002D-02 -0.940281D-02 0.221956D+00 0.191970D+01
6 -0.101400D-01 -0.178752D-02 -0.705884D-01 -0.453979D+00 0.492118D+00
7 0.961588D-01 -0.872428D-02 -0.555307D-01 -0.404556D-01 0.394086D-01
6
7
6 0.447165D+00
7 0.472548D-02 0.130499D+00
Final State Averaged Density Matrix
1
2
3
4
5
1 0.195695D+01
2 0.813892D-07 0.198990D+01
3 0.119409D-06 -0.353870D-08 0.192162D+01
4 0.193519D-06 0.673171D-07 0.116832D-07 0.169477D+01
5 -0.971412D-06 0.264017D-06 0.912963D-07 0.730008D-08 0.154253D+01
6 0.307912D-06 0.157249D-06 0.224956D-07 0.171035D-07 -0.219905D-06
7 -0.860620D-06 0.187179D-06 0.322083D-07 0.445070D-06 0.899281D-07
6
7
6 0.737007D+00
7 0.349897D-06 0.157216D+00
Ecx terms are ignored for the Tr den
1
Ecx terms are ignored for the Tr den
2
In PrCiAS Ecx terms are ignored for the Tr den
1
In PrCiAS Ecx terms are ignored for the Tr den
2
Ecx terms are ignored for the Tr den
1
Ecx terms are ignored for the Tr den
2
MCSCF converged.
……
……
……
Variable
Old X
R1
R2
R3
R4
R5
R6
R7
R8
R9
R10
R11
A1
A2
A3
A4
A5
A6
2.54271
2.60722
1.87872
2.45179
2.02272
2.53684
2.54011
5.33394
2.01522
2.26346
2.39028
1.87272
2.20235
2.20811
1.95784
2.13755
2.18780
-DE/DX
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
Delta X
(Linear)
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
Delta X
(Quad)
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
13
Delta X
(Total)
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
0.00000
New X
2.54271
2.60722
1.87872
2.45179
2.02272
2.53684
2.54011
5.33394
2.01522
2.26346
2.39028
1.87272
2.20235
2.20811
1.95784
2.13755
2.18780
A7
A8
A9
A10
A11
A12
A13
A14
A15
A16
D1
D2
D3
D4
D5
D6
D7
D8
D9
D10
D11
D12
D13
D14
D15
D16
D17
D18
D19
D20
1.81484
0.00000
0.00000
0.00000
0.00000
1.98331
0.00000
0.00000
0.00000
0.00000
1.65387
0.00000
0.00000
0.00000
0.00000
2.62382
0.00000
0.00000
0.00000
0.00000
1.79606
0.00000
0.00000
0.00000
0.00000
2.15447
0.00000
0.00000
0.00000
0.00000
2.33266
0.00000
0.00000
0.00000
0.00000
2.08872
0.00000
0.00000
0.00000
0.00000
0.89254
0.00000
0.00000 -0.00001 -0.00001
2.07661
0.00000
0.00000
0.00001
0.00001
0.00036
0.00000
0.00000
0.00000
0.00000
-3.14144
0.00000
0.00000
0.00000
0.00000
3.14156
0.00000
0.00000
0.00000
0.00000
-0.00024
0.00000
0.00000
0.00000
0.00000
0.00025
0.00000
0.00000
0.00000
0.00000
3.14117
0.00000
0.00000
0.00000
0.00000
-3.14095
0.00000
0.00000
0.00000
0.00000
-0.00003
0.00000
0.00000
0.00000
0.00000
-0.00079
0.00000
0.00000
0.00001
0.00001
3.14101
0.00000
0.00000
0.00000
0.00000
0.00099
0.00000
0.00000 -0.00001 -0.00001
-2.98688
0.00000
0.00000 -0.00001 -0.00001
-0.00077
0.00000
0.00000
0.00001
0.00001
-3.14159
0.00000
0.00000
0.00000
0.00000
2.82742
0.00000
0.00000
0.00000
0.00000
-0.31339
0.00000
0.00000
0.00000
0.00000
-0.87953
0.00000
0.00000
0.00000
0.00000
-2.71027
0.00000
0.00000
0.00000
0.00000
2.54941
0.00000
0.00000
0.00001
0.00001
0.71867
0.00000
0.00000
0.00000
0.00000
Item
Value
Threshold Converged?
Maximum Force
0.000003
0.000015
YES
RMS
Force
0.000001
0.000010
YES
Maximum Displacement
0.000018
0.000060
YES
RMS
Displacement
0.000004
0.000040
YES
Predicted change in Energy=-3.081748D-11
Optimization completed.
-- Stationary point found.
1.81484
1.98331
1.65387
2.62382
1.79606
2.15447
2.33266
2.08873
0.89253
2.07662
0.00035
-3.14144
3.14155
-0.00024
0.00024
3.14117
-3.14095
-0.00003
-0.00079
3.14101
0.00098
-2.98689
-0.00076
-3.14159
2.82742
-0.31340
-0.87953
-2.71027
2.54942
0.71868
……
……
……
Total kinetic energy from orbitals= 4.273799291037D+02
No NMR shielding tensors so no spin-rotation constants.
Leave Link 601 at Thu Dec 29 19:32:13 2011, MaxMem= 524288000 cpu:
(Enter /home/diag/opt/gaussian/g09/l9999.exe)
1\1\GINC-TRESTLES-1-10\FOpt\CASSCF\6-31G(d)\C3H3N3O2\ZJYU\29-Dec-2011\
0\\#p opt=(conical,maxcycle=100,tight) CASSCF(10,7,nroot=2)/6-31g(d) g
uess=read geom=check scf=(maxcycle=2000) pop=full gfinput nosymm\\read
from S1S0CIffff\\0,1\N,-2.6110224254,0.4970918444,-0.0166496916\C,-2.
1483172767,-0.5297253356,-0.7528801971\N,-0.8568877797,-0.6360974553,0.6879052997\C,-0.4891488696,0.3679015187,0.1238144512\C,-1.5207834589
,1.1035742249,0.5724837155\H,-3.5628900006,0.7664818967,0.0821363943\H
,-2.794785066,-1.169325579,-1.3174095839\H,-1.5958581198,1.9515609288,
1.2147539801\N,2.2751939796,0.0533738533,-0.3521485294\O,2.7749356389,
-1.030374434,-0.2501416464\O,1.6951839282,0.5578077872,0.6523746569\\V
ersion=AM64L-G09RevC.01\HF=-428.2104507\RMSD=0.000e+00\RMSF=8.890e-07\
Dipole=-1.6133346,0.7618889,0.2062003\Quadrupole=8.3908645,-3.9169975,
-4.473867,-0.4053755,0.4996439,1.0892296\PG=C01 [X(C3H3N3O2)]\\@
1.1
I CLAIM NOT TO HAVE CONTROLLED EVENTS,
BUT CONFESS PLAINLY THAT EVENTS HAVE CONTROLLED ME.
A. LINCOLN
Job cpu time: 1 days 10 hours 41 minutes 12.7 seconds.
File lengths (MBytes): RWF=
557 Int=
0 D2E=
14
0 Chk=
3 Scr=
1
5. IRC from the conical intersection
Here we gives a simply description of how to do an IRC calculation from a conical
intersection.
At a TS there is a transition vector along the reaction coordinate and one can define forward
and reverse directions along that reaction coordinate. From a conical intersection there is no a
reaction coordinate defined. Instead, there is one “downhill” direction on one electronic state,
and there is another downhill direction on the other electronic state.
1) Perform an "Opt=Conical" with tight convergence criteria.
#p opt=(conical, maxcycle=100, tight) CASSCF(10, 7, nroot=2)/6-31g(d) guess=read geom=check
scf=(maxcycle=2000) pop=full gfinput nosymm
2) Follow the downhill path for the lowest of the two roots in the conical intersection found in
step 1. Make a copy of the checkpoint file from the conical intersection found in step 1, and use
keyword “iop(5/97=100,10/97=100)” to Flip roots 1 and 2, This is the way to be able to follow
the lowest root in a state-average CAS calculation.
Output file:
Summary of reaction path following
-------------------------------------------------------------------------Energy RxCoord
1
-428.21049 0.00000
2
-428.21255 0.04995
3
-428.21448 0.09994
4
-428.21628 0.14992
5
-428.21795 0.19991
6
-428.21952 0.24989
7
-428.22098 0.29987
8
-428.22235 0.34986
9
-428.22365 0.39984
10
-428.22487 0.44982
11
-428.22605 0.49979
12
-428.22720 0.54977
13
-428.22965 0.59969
14
-428.23053 0.64964
15
-428.23136 0.69961
16
-428.23215 0.74959
17
-428.23292 0.79956
15
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
-428.23367
-428.23440
-428.23513
-428.23585
-428.23657
-428.23729
-428.23802
-428.23874
-428.23948
-428.24022
-428.24096
-428.24172
-428.24315
-428.24457
-428.24599
-428.24741
-428.24884
-428.25028
-428.25174
-428.25319
-428.25459
-428.25641
-428.25734
-428.25827
-428.25921
-428.26016
-428.26112
-428.26208
-428.26306
-428.26404
-428.26503
-428.26603
-428.26704
-428.26806
-428.26908
-428.27011
-428.27115
-428.27220
-428.27325
-428.27431
-428.27538
-428.27645
-428.27753
-428.27862
-428.27971
-428.28081
-428.28191
-428.28302
-428.28414
-428.28525
-428.28638
-428.28750
-428.28864
-428.28977
-428.29091
-428.29205
0.84953
0.89951
0.94949
0.99947
1.04946
1.09944
1.14943
1.19942
1.24940
1.29939
1.34938
1.39937
1.44936
1.49935
1.54934
1.59933
1.64932
1.69931
1.74930
1.79929
1.84927
1.89926
1.94925
1.99924
2.04923
2.09922
2.14921
2.19920
2.24919
2.29918
2.34917
2.39916
2.44915
2.49914
2.54913
2.59912
2.64911
2.69910
2.74909
2.79908
2.84907
2.89906
2.94905
2.99904
3.04903
3.09902
3.14901
3.19900
3.24899
3.29898
3.34897
3.39896
3.44895
3.49894
3.54893
3.59892
16
74
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
-428.29319
-428.29433
-428.29548
-428.29662
-428.29777
-428.29892
-428.30006
-428.30121
-428.30235
-428.30350
-428.30463
-428.30577
-428.30690
-428.30803
-428.30915
-428.31027
-428.31138
-428.31248
-428.31358
-428.31467
-428.31575
-428.31682
-428.31787
-428.31892
-428.31996
-428.32098
-428.32199
-428.32299
3.64891
3.69890
3.74889
3.79888
3.84887
3.89886
3.94885
3.99884
4.04883
4.09882
4.14881
4.19880
4.24879
4.29878
4.34877
4.39876
4.44875
4.49874
4.54873
4.59872
4.64871
4.69870
4.74869
4.79868
4.84867
4.89866
4.94865
4.99864
3) Move away from the conical intersection barely enough to make the other electronic state
become the new ground state. Now we need to follow downhill the other electronic state
(root=2); however, as we step downhill away from the conical intersection on the surface of
"root=2", the order of the two roots will change, i.e. what is now "root=2" will become lower in
energy than what is currently "root=1". This will become a problem because at the second step,
the IRC will try to follow the other electronic state. Thus, what we need to do at this point is
taking only one step downhill away from the conical intersection, enough to make "root=2"
become "root=1". After that step, the situation will be identical than in point 2) described above.
So, we would make another copy of the checkpoint file from point 1) and use it for a job like the
following:
17
%chk=IRCS1S0b.chk
%mem=12000MB
%nprocshared=4
#p casscf(10,7,nroot=2, stateaverage)/6-31g(d) irc=(calcall, downhill, step=-5,maxpoints=1,recorrect=never)
geom=check guess=read nosymm
read from orbitals from step 1, move one step away from CI
01
So, an IRC downhill on the surface of "root=2" taking only one step with the smallest step size
and without using the "recorrect" procedure. This will move away from the conical intersection,
just enough to change the order of the two electronic states.
4) Finally, follow downhill the other electronic state. At this point, after 3), the second
electronic state is now ground state, so from here we just need to proceed as described in point 2)
above; i.e. the IRC that follows the ground state downhill.
Output file:
Energies reported relative to the TS energy of
0.000000
-------------------------------------------------------------------------Summary of reaction path following
-------------------------------------------------------------------------Energy RxCoord
1
-428.21234 0.00000
2
-428.21416 0.04999
3
-428.21589 0.09998
4
-428.21750 0.14996
5
-428.21899 0.19995
6
-428.22037 0.24993
7
-428.22162 0.29991
8
-428.22276 0.34988
9
-428.22379 0.39984
10
-428.22472 0.44980
11
-428.22556 0.49976
12
-428.22633 0.54972
13
-428.22703 0.59968
14
-428.22768 0.64964
15
-428.22828 0.69961
16
-428.22885 0.74958
17
-428.22938 0.79956
18
-428.22989 0.84954
18
19
20
21
22
23
24
25
26
27
28
29
30
31
32
33
34
35
36
37
38
39
40
41
42
43
44
45
46
47
48
49
50
51
52
53
54
55
56
57
58
59
60
61
62
63
64
65
66
67
68
69
70
71
72
73
74
-428.23037
-428.23082
-428.23126
-428.23169
-428.23209
-428.23340
-428.23461
-428.23571
-428.23672
-428.23764
-428.23846
-428.23919
-428.23982
-428.24033
-428.24071
-428.24099
-428.24128
-428.24155
-428.24182
-428.24209
-428.24235
-428.24261
-428.24286
-428.24310
-428.24335
-428.24358
-428.24382
-428.24405
-428.24427
-428.24449
-428.24470
-428.24492
-428.24512
-428.24533
-428.24553
-428.24572
-428.24592
-428.24610
-428.24629
-428.24647
-428.24665
-428.24682
-428.24699
-428.24716
-428.24732
-428.24748
-428.24764
-428.24779
-428.24795
-428.24809
-428.24824
-428.24838
-428.24852
-428.24866
-428.24879
-428.24892
0.89951
0.94949
0.99947
1.04945
1.09943
1.14942
1.19940
1.24939
1.29937
1.34935
1.39934
1.44933
1.49931
1.54930
1.59929
1.64927
1.69926
1.74925
1.79924
1.84923
1.89922
1.94921
1.99920
2.04919
2.09918
2.14917
2.19916
2.24915
2.29914
2.34913
2.39912
2.44911
2.49910
2.54909
2.59908
2.64907
2.69906
2.74905
2.79904
2.84903
2.89902
2.94901
2.99900
3.04900
3.09899
3.14898
3.19897
3.24896
3.29895
3.34894
3.39893
3.44892
3.49891
3.54890
3.59889
3.64888
19
75
76
77
78
79
80
81
82
83
84
85
86
87
88
89
90
91
92
93
94
95
96
97
98
99
100
101
-428.24905
-428.24918
-428.24930
-428.24942
-428.24954
-428.24965
-428.24977
-428.24988
-428.24999
-428.25009
-428.25020
-428.25030
-428.25040
-428.25049
-428.25059
-428.25068
-428.25077
-428.25086
-428.25095
-428.25104
-428.25112
-428.25120
-428.25128
-428.25136
-428.25144
-428.25151
-428.25158
3.69887
3.74886
3.79885
3.84884
3.89883
3.94882
3.99881
4.04880
4.09879
4.14878
4.19877
4.24876
4.29875
4.34874
4.39873
4.44872
4.49871
4.54870
4.59869
4.64868
4.69867
4.74866
4.79865
4.84864
4.89864
4.94863
4.99862
20