Supporting Information
Spectroscopy and Photochemistry of Triplet 1,3-Dimethylpropynylidene
(MeC3Me)
Stephanie N. Knezz, Terese A. Waltz, Benjamin C. Haenni, Nicola J. Burrmann,
and Robert J. McMahon*
Department of Chemistry, University of Wisconsin-Madison, 1101 University Avenue, Madison,
Wisconsin 53706-1322, United States
Email: [email protected]
Experimental Methods .............................................................................................................. S2
Figure S1. Computed Relative Energies of C5H6 Isomers .......................................................... S3
Figure S2. Computed Structures of C5H6 Isomers ...................................................................... S4
References ................................................................................................................................... S5
Figures S3-S8. Matrix Isolation Spectra .............................................................................. S6-S11
Tables S1-S2. Experimental IR Data ................................................................................ S12-S13
1
H and 13C NMR Spectra ................................................................................................. S14-S21
Tables of Computational Data. Cartesian coordinates, absolute energies, harmonic vibrational
frequencies for computed structures at various levels of theory ......................................... S22-S42
S1
Experimental Methods. The matrix isolation apparatus and technique have been
described previously.1,2 Irradiation was carried out with an ILC Technology LX300UV 300 W
high-pressure xenon arc lamp, and wavelength selection was achieved with cut-off filters (λ >
613 nm, Corning 2-58; λ > 534, Corning 3-66; λ > 497 nm, Corning 3-69; λ > 472 nm, Corning
3-71; λ > 444 nm, Corning 3-72; λ > 399 nm, Corning 3-74; λ > 363 nm, Corning 3-75; λ > 328
nm, Schott WG 345; λ > 300 nm, Schott WG 320; λ > 280 nm, Pyrex; λ > 261 nm; Corning 053; λ > 237 nm, Corning 0-56) or a Spectral Energy GM 252 monochromator (bandpass of 20
nm). All IR spectra were recorded on a Nicolet Nexus 870 FT-IR spectrometer with a DTGS
detector. Electronic spectra were recorded with a Varian Cary 5000 UV/vis/NIR
spectrophotometer utilizing a spectral bandwidth of 2.0 nm. EPR spectra were obtained on a
Bruker EleXsys E-500-A EPR spectrometer consisting of: Bruker ER 049SX X-band
microwave bridge (Gunn diode), ER 041-1161 microwave frequency meter, and high-sensitivity
resonator with optical port. EPR zero-field splitting parameters were determined by a best fit of
the observed spectrum to the spin Hamiltonian utilizing the assumption gx = gy = ge.3
Isomerization of MeC3Me (3) to Pent-1-en-3-yne (4). Experiments described in the
body of the article establish the isomerization of triplet MeC3Me (33) to pent-1-en-3-yne (4)
under photochemical conditions. To gain a more thorough understanding of the reactivity scope,
we sought to determine whether the H-shift isomerization might also occur on the ground state
through a tunneling mechanism. After generating matrix isolated MeC3Me (33), the sample was
left in the dark at 12 K. No changes were observed in either IR or UV/vis spectra after 24 h,
indicating that a tunneling process is occurring. In order to see if temperature affected the
reactivity, an annealing experiment was carried out. The temperature of the matrix was increased
by 5 K every hour, and an IR spectrum was obtained (Figure S5). This experiment was largely
inconclusive due to the poor spectral quality at higher temperatures. Although it appears that
triplet MeC3Me (3) is disappearing, signature bands of enyne 4 were not observed.
S2
H3C
C
C C
H3C
CH3
C
3
CH3
6
C2v
C1
C1
53.0 (T1 0.016)
H3C
C C C
H3C
3
3
5
H3C
C
C
26.1 (T1 0.017)
47.1 (T1 0.056)
C1
50.9
C1
C2v
21.2
48.9
C
C C
H3C C C C CH3
CH3
3
5
C2v
3
Cs
14.4 (T1 0.032)
0.0 (T1 0.010)
Cs
H3C
C
C
14.5 (T1 0.015)
C2v
D3
8.4
0.0
H3C
C C C
H3C
6
C2v
14.6
H
C
CH2
CCSD/cc-pVDZ
4
Cs
-32.5 (T1 0.011)
B3LYP/6-31G(d)
Cs
-33.0
Figure S1. Computed relative energies of selected C5H6 isomers (kcal/mol; includes ZPVE).
Above in blue: CCSD/cc-pVDZ (T1 diagnostic in parenthesis). Below in red: B3LYP/6-31G(d).
Relative energies for isomers 4, 5, and 6, computed using DFT methods (B3LYP/6-31G(d))
show qualitatively good agreement with the CCSD values, but the energies for the delocalized
carbon chain isomer, MeC3Me (13, 33), are too low, reflecting the well-established problem of
the B3LYP functional in over-stabilizing delocalized systems of this type.4-6
The T1 value for triplet MeC3Me (33) is 0.032, which may be considered just a bit high –
indicative of multireference character.7,8 It is known that higher order excitation levels can
correct for some amount of multireference character.9 We are confident in suitability and
reliability of our calculations at the CCSD(T) level.
S3
Figure S2. Computed structures for MeC3Me (3) and MeC3H (12). (a) 33 at
B3LYP/6-31G(d) (D3). (b) 33 at CCSD/cc-pVDZ (Cs). (c) 13 at CCSD/ccpVDZ (C1). (d) 33 at CCSD(T)/ANO1 (C1). (e) 312 at B3LYP/6-31G(d) (Cs).
(f) 312 at CCSD/cc-pVDZ (Cs).
S4
References
1.
"Mechanistic studies on the Wolff rearrangement: the chemistry and spectroscopy of
some a-keto carbenes" McMahon, R. J.; Chapman, O. L.; Hayes, R. A.; Hess, T. C.;
Krimmer, H. P. J. Am. Chem. Soc. 1985, 107, 7597-7606.
2.
"Photochemistry of matrix-isolated diazoethane and methyldiazirine: ethylidene
trapping?" Seburg, R. A.; McMahon, R. J. J. Am. Chem. Soc. 1992, 114, 7183-7189.
3.
"ESR of the Triplet States of Randomly Oriented Molecules" Wasserman, E.; Snyder, L.
C.; Yager, W. A. J. Chem. Phys. 1964, 41, 1763-1772.
4.
"C18 Is a Polyyne" Plattner, D. A.; Houk, K. N. J. Am. Chem. Soc. 1995, 117, 4405-4406.
5.
"Structures and Stabilities of C5H2 Isomers: Quantum Chemical Studies" Seburg, R. A.;
McMahon, R. J.; Stanton, J. F.; Gauss, J. J. Am. Chem. Soc. 1997, 119, 10838-10845.
6.
"Problematic Energy Differences between Cumulenes and Poly-ynes: Does This Point to
a Systematic Improvement of Density Functional Theory?" Woodcock, H. L.; Schaefer,
H. F., III; Schreiner, P. R. J. Phys. Chem. A 2002, 106, 11923-11931.
7.
"A Diagnostic for Determining the Quality of Single-Reference Electron Correlation
Methods" Lee, T. J.; Taylor, P. R. Int. J. Quantum Chem. 1989, S23, 199-207.
8.
"Comparison of the T1 and D1 diagnostics for electronic structure theory: a new definition
for the open-shell D1 diagnostic" Lee, T. J. Chem. Phys. Lett. 2003, 372, 362–367.
9.
"Problematic p-benzyne: Orbital instabilities, biradical character, and broken symmetry"
Crawford, T. D.; Kraka, E.; Stanton, J. F.; Cremer, D. J. Chem. Phys. 2001, 114, 1063810650.
S5
Figure S3. Above: Computed IR spectra for triplet MeC3Me (33) at CCSD(T)/ANO1 (top) and
B3LYP/6-31G(d) (below). Middle: IR subtraction spectrum showing the disappearance of 2-diazo-3pentyne (11) and appearance of triplet MeC3Me (33) upon irradiation (λ > 472 nm, 6 h, N2, 10 K).
Bottom: Computed IR spectrum for 2-diazo-3-pentyne (11) (CCSD/cc-pVDZ).
S6
Figure S4. Top: Computed IR spectrum for diazirine (B3LYP/6-31G(d)). Middle: IR subtraction
spectrum showing the disappearance of 2-diazo-3-pentyne (11) and appearance of photoproduct, assigned
as triplet MeC3Me (33), upon irradiation (λ > 472 nm, 6 h, N2, 10 K). Bottom: Computed IR spectrum for
2-diazo-3-pentyne (11) (CCSD/cc-pVDZ). Comparison of experimental and predicted IR absorptions
establishes that the diazirine is not the photoproduct obtained upon irradiation of 2-diazo-3-pentyne (11).
S7
Figure S5. Above: Computed IR spectrum of pent-1-en-3-yne (4) (CCSD(T)/ANO1) (top) and
authentic IR spectrum of matrix isolated pent-1-en-3-yne (4) (N2, 10 K) (bottom). Middle: IR
subtraction spectrum showing the disappearance of triplet MeC3Me (33) and appearance of pent-1-en-3yne (4) upon irradiation (λ > 330 nm, 24 h, N2, 10 K). Bottom: Computed IR spectrum of triplet
MeC3Me (33) (B3LYP/cc-pVTZ).
S8
Figure S6. IR difference spectra for the annealing experiment with MeC3Me (33). A matrix containing
3
3 (N2, 10 K) was subjected to increasing temperatures (15 K to 65 K; matrix melts above ca. 40 K),
and IR spectra were acquired at 5 K increments. Difference spectra were obtained by subtracting the
t = 0 spectrum (15 K) from each successive spectrum.
S9
Figure S7. Solution phase electronic absorption spectrum of 2-diazo-3-pentyne (11) in MeOH at
298 K. Top: Full spectrum revealing λmax= 250 nm. Bottom: Expansion revealing λmax = 512 nm.
Spectra taken of samples obtained upon a series of dilutions. (Actual concentration unknown)
S10
Absorbance
2.0
1.5
1.0
0.5
200
300
400
500
600
700
800
Wavelength (nm)
Figure S8. Electronic absorption spectrum of 2-diazo-3-pentyne (11) (red spectrum) after sample deposition
(5 min, N2, 10 K) and after irradiation (λ > 472 nm, 16 h; N2, 10 K) (cyan spectrum).
S11
Table S1. Experimentally observed IR frequencies and intensities. Intensities are normalized
relative to the most intense band (=100).
MeC3Me (33)
Frequency (cm-1) Relative intensity
2931
16
2897
100
2830
74
2725
35
1443
1429
1369
1311
46
84
39
20
1002
16
2-diazo-3-pentyne (11)
Frequency (cm-1) Relative intensity
2965
7
2928
10
2901
7
2860
8
S12
2199
2067
2004
1466
1439
1386
5
100
6
6
13
10
1039
664
6
6
Table S2. Experimentally observed IR frequencies and intensities. Intensities are normalized
relative to the most intense band (=100).
MeC3Me isomerization
product
Frequency (cm-1)
Relative intensity
2984
2933
2866
2349
2249
1842
1724
1615
1597
1444
1415
1365
1270
1174
1096
1033
977
918
674
21
17
31
28
62
10
34
93
59
100
62
3
31
38
3
7
100
86
3
Pent-1-en-3-yne (4)
Authentic sample
Frequency (cm-1)
Relative intensity
2976
2925
2862
2341
2241
1848
1716
1613
1598
1443
1415
1387
1295
1170
1071
1028
982
929
680
S13
81
42
19
16
71
8
7
100
42
77
31
25
15
47
32
24
100
100
28
S14
S15
O
S
O
HN
NH2
S16
S17
S18
S19
S20
S21
Charge Multiplicity Theory/Basis Set 0 Zero‐point Energy 0.099367 1 Electronic Energy ‐302.654829 RCCSD(FC)/CC‐pVDZ Electronic and Zero‐Point Energy ‐302.555462 ΔH(298) ‐302.545839 ΔG(298) ‐302.591045 Energies in Hartrees/particle Full Point Group C1 Dipole Moment (D) 1.5524 Symmetry A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A Vibrational Frequency (cm‐1) 8.2896 88.5011 95.4316 129.5585 216.0075 247.7393 292.9530 416.4959 462.9027 505.4150 559.4455 676.2751 957.4038 1052.9533 1054.4273 1059.0363 1063.3779 1335.5014 1395.2268 1422.4282 1427.0730 1471.9113 1478.7383 1485.0457 1509.0362 2166.5794 2334.7833 3057.3419 3065.1219 3131.4051 3145.4398 3149.3786 3155.8521 Intensity 0.0031 1.5736 0.6774 4.9196 3.6561 0.8929 2.3174 1.7875 0.7433 7.0430 2.8880 9.0569 4.7449 0.2372 0.7768 0.2634 9.9524 1.5636 7.3408 7.9860 13.7070 6.1676 5.4774 6.6318 9.2008 717.5782 1.4642 39.3740 35.9991 18.0510 11.4626 9.2801 12.7976 S22
Atom C H H H C C C C H H H N N Coordinates (Angstroms) X Y Z ‐3.293382 ‐0.259282 0.000033 ‐3.615920 ‐0.839024 ‐0.882494 ‐3.808660 0.716699 ‐0.025533 ‐3.622622 ‐0.796012 0.906971 ‐1.829955 ‐0.063717 0.000120 ‐0.612405 0.086929 0.000055 0.801394 0.335610 0.000030 1.413229 1.721270 ‐0.000022 1.100298 2.289733 0.894656 2.514902 1.655773 0.000290 1.100789 2.289513 ‐0.895015 1.604369 ‐0.709801 ‐0.000010 2.318192 ‐1.610419 ‐0.000014 Charge Multiplicity Theory/Basis Set 0 Zero‐point Energy 0.099228 1 Electronic Energy ‐303.509597034 RB3LYP/6‐31G(d) Electronic and Zero‐Point Energy ΔH(298) ΔG(298) Energies in Hartrees/particle Full Point Group C1 Dipole Moment (D) Symmetry A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A A Vibrational Frequency (cm‐1) 9.8824 15.4629 127.8087 146.9950 307.1072 321.8034 363.1029 390.4999 547.4376 551.0231 627.0961 809.4583 895.2419 1061.0921 1067.5623 1067.9954 1094.0253 1188.5234 1301.3133 1440.6459 1443.8366 1504.2149 1506.8063 1509.9790 1520.1537 1724.2768 2359.7047 3041.0543 3055.1069 3102.3571 3104.9867 3118.0401 3141.5016 Intensity 0.0254 2.0486 0.3749 1.8503 3.2239 2.1463 4.0242 0.3135 4.0897 0.0009 8.9089 1.1165 3.6443 7.4363 2.4628 2.3854 0.3209 3.6953 21.9741 0.5270 10.4016 7.4985 6.7933 4.9174 8.7621 74.756 10.4268 27.7198 16.2373 10.1060 9.6989 14.8753 12.1383 S23
Atom C N N C C C H H H C H H H Coordinates (Angstroms) X Y Z 0.913868 0.100399 ‐0.000014 1.655272 ‐1.043143 0.614112 1.655268 ‐1.043167 ‐0.614099 ‐0.519388 0.030947 ‐0.000008 ‐1.730367 0.005854 ‐0.000002 1.580814 1.455640 ‐0.000003 1.288264 2.029175 ‐0.886826 1.288315 2.029135 0.886863 2.669154 1.345937 ‐0.000010 ‐3.188968 ‐0.036285 0.000006 ‐3.571773 ‐0.556925 0.886151 ‐3.611750 0.975504 ‐0.000608 ‐3.571742 ‐0.557984 ‐0.885530 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.089986 
1 Electronic Energy ‐194.060614 
RB3LYP/6‐31G(d) Electronic and Zero‐Point Energy ‐193.970627 (Energies in Hartrees/particle) CS Dipole Moment (D) 0.6045 Symmetry A" A' A" A' A" A' A" A' A" A" A' A" A' A' A' A' A' A' A" A' A' A' A" A' A' A' A' Vibrational Frequency (cm‐1) 16.1372 144.0493 194.1898 325.7827 385.9595 535.7414 708.4695 727.9513 931.9777 1014.2225 1056.2112 1066.4481 1071.3344 1207.2293 1336.5380 1443.2343 1468.1904 1506.4794 1506.4924 1692.1314 2347.9998 3035.7143 3094.0766 3099.0547 3148.1752 3175.2328 3260.4516 Intensity 0.0001 3.4980 6.5539 2.2975 0.0591 1.3926 4.2016 2.3108 35.4723 15.4082 1.2803 2.9244 1.5316 4.2920 1.5947 8.2237 2.7195 5.7230 5.8922 16.2846 13.0037 34.9668 12.8896 12.7544 15.3706 5.5192 12.8608 S24
Atom C C C C C H H H H H H Coordinates (Angstroms) X Y Z 2.422624 ‐0.887804 0.000000 1.104379 ‐0.262344 0.000000 0.000000 0.239648 0.000000 ‐1.272171 0.879401 0.000000 ‐2.452231 0.240672 0.000000 ‐2.515695 ‐0.843378 0.000000 ‐3.385703 0.795116 0.000000 ‐1.260648 1.969863 0.000000 3.221241 ‐0.136079 0.000000 2.562599 ‐1.521480 0.884767 2.562599 ‐1.521480 ‐0.884767 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.089750 
1 Electronic Energy ‐193.471687 
RCCSD(FC)/CC‐pVDZ Electronic and Zero‐Point Energy ‐193.381937 (Energies in Hartrees/particle) CS Dipole Moment (D) 0.4666 Symmetry A" A' A" A' A" A' A" A' A" A" A' A" A' A' A' A' A' A" A' A' A' A' A" A' A' A' A' Vibrational Frequency (cm‐1) 15.1917 136.2971 185.2947 304.1112 345.9035 515.1022 673.1813 720.8745 934.1771 999.5445 1047.5188 1055.4706 1059.5265 1196.0143 1319.8217 1419.5687 1450.1852 1481.8177 1481.8276 1695.2016 2338.6735 3067.6809 3149.7050 3151.9363 3177.3888 3194.2885 3279.5898 Intensity 0.0037 3.6457 7.4018 2.2895 0.0571 1.8429 3.7927 1.6871 27.0062 20.1799 0.3764 1.2406 0.4679 4.9115 2.6994 8.0525 3.2047 6.0758 5.7824 12.4119 7.9938 29.6427 9.9660 9.8611 3.3654 10.5057 9.4070 S25
Atom C H H H C C C H C H H Coordinates (Angstroms) X Y Z ‐2.450722 ‐0.889956 0.000000 ‐3.246096 ‐0.124828 0.000000 ‐2.582189 ‐1.524071 0.893998 ‐2.582189 ‐1.524071 ‐0.893998 ‐1.116352 ‐0.257351 0.000000 0.000000 0.249150 0.000000 1.296377 0.893112 0.000000 1.295340 1.991073 0.000000 2.469365 0.220933 0.000000 2.500504 ‐0.874361 0.000000 3.422621 0.760930 0.000000 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.089171 
1 Electronic Energy ‐194.007172 
RB3LYP/6‐31G(d) Electronic and Zero‐Point Energy ‐193.918001 (Energies in Hartrees/particle) CS Dipole Moment (D) 3.7680 Symmetry A' A" A' A' A" A" A' A" A' A' A" A" A" A' A" A' A" A' A" A' A' A" A' A" A' A' A" Vibrational Frequency (cm‐1) 30.5284 38.6502 203.5556 290.1407 418.5789 494.9932 737.1781 777.7978 1015.2927 1024.8081 1065.6417 1102.4049 1287.6780 1334.2131 1423.7411 1425.7850 1498.1642 1502.2503 1513.9156 1514.1028 1867.8545 3047.4458 3048.1442 3109.7390 3110.0147 3129.4117 3129.4294 Intensity 2.4613 0.4590 2.9385 2.8430 5.0173 0.0025 0.7744 4.7264 7.8230 6.5130 2.4227 1.2923 28.4391 12.1408 2.1995 4.7357 3.5127 18.9862 3.2358 12.7362 6.4545 20.6637 6.2243 7.4343 19.1940 12.2049 10.8485 S26
Atom C C C C H H H C H H H Coordinates (Angstroms) X Y Z ‐0.004631 0.178966 0.667459 ‐0.004631 0.178966 ‐0.667459 0.001293 1.438152 0.000000 ‐0.004631 ‐0.536788 1.965082 ‐0.409983 0.095205 2.761900 ‐0.567797 ‐1.475225 1.917943 1.029470 ‐0.787508 2.234449 ‐0.004631 ‐0.536788 ‐1.965082 ‐0.567797 ‐1.475225 ‐1.917943 ‐0.409983 0.095205 ‐2.761900 1.029470 ‐0.787508 ‐2.234449 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.089280 
1 Electronic Energy ‐193.419405 
RCCSD(FC)/CC‐pVDZ Electronic and Zero‐Point Energy ‐193.330125 (Energies in Hartrees/particle) C2V Dipole Moment (D) 3.6459 Symmetry B1 A2 A1 B1 B2 A2 A1 B2 B1 A1 A2 B2 A1 B2 A1 B2 B2 A1 B1 A2 A1 B2 A1 B1 A2 B2 A1 Vibrational Frequency (cm‐1) 25.0483 33.5544 200.3572 283.7522 409.9671 484.1120 736.5799 781.0166 1016.4258 1028.5564 1047.9796 1083.4381 1318.4104 1323.7716 1403.8035 1410.8022 1475.9257 1480.5270 1480.7773 1481.6296 1901.5468 3069.6767 3070.3731 3153.1812 3153.2745 3167.3386 3167.5837 Intensity 5.8412 0.0000 3.0262 3.6972 4.3149 0.0000 0.7720 4.2801 3.9243 3.3819 0.0000 5.6692 21.6649 19.4767 0.7602 8.6955 12.4164 13.3212 13.2982 0.0000 1.4958 21.1712 8.7640 9.6812 0.0000 0.0116 24.7782 S27
Atom C C C C H H H C H H H Coordinates (Angstroms) X Y Z 0.000000 0.672408 0.168210 0.000000 ‐0.672408 0.168210 0.000000 0.000000 1.442769 0.000000 1.984315 ‐0.540206 0.888343 2.562124 ‐0.229579 0.000000 1.874753 ‐1.637169 ‐0.888343 2.562124 ‐0.229579 0.000000 ‐1.984315 ‐0.540206 0.000000 ‐1.874753 ‐1.637169 0.888343 ‐2.562124 ‐0.229579 ‐0.888343 ‐2.562124 ‐0.229579 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.087449 
3 Electronic Energy ‐193.924394 
UB3LYP/6‐31G(d) Electronic and Zero‐Point Energy ‐193.836946 (Energies in Hartrees/particle) C1 Dipole Moment (D) 2.3398 Symmetry A A A A A A A A A A A A A A A A A A A A A A A A A A A Vibrational Frequency (cm‐1) 134.5975 141.1909 166.3035 277.1760 375.8948 407.9503 591.0065 792.7780 947.6996 1036.1626 1047.2316 1062.9606 1074.0871 1269.2397 1416.4149 1432.3522 1494.5186 1496.9524 1503.3602 1507.5475 1820.1088 2988.9430 3030.8719 3072.8031 3087.0589 3101.0843 3109.1783 Intensity 0.4573 0.4380 3.3291 1.2797 5.2919 0.2519 12.6971 9.0163 4.3254 1.7279 8.4155 3.5493 1.2214 34.8902 2.0163 1.6811 8.8875 9.9731 9.8052 4.5064 5.1272 42.7778 26.4770 19.5595 11.1633 16.5197 10.1527 S28
Atom C C C C H H H C H H H Coordinates (Angstroms) X Y Z ‐0.794527 0.879015 ‐0.150706 ‐0.436172 ‐0.608554 0.227757 ‐1.027577 0.184153 1.083264 0.159868 ‐1.812445 ‐0.368750 ‐0.376131 ‐2.105392 ‐1.281493 1.209174 ‐1.644605 ‐0.642332 0.120170 ‐2.649101 0.338731 0.113039 1.983627 ‐0.584612 0.262791 1.975591 ‐1.670795 ‐0.330353 2.952918 ‐0.322871 1.102589 1.924815 ‐0.101829 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.088037 
3 Electronic Energy ‐193.333822 
UCCSD(FC)/CC‐pVDZ Electronic and Zero‐Point Energy ‐193.245785 (Energies in Hartrees/particle) C1 Dipole Moment (D) 2.3783 Symmetry A A A A A A A A A A A A A A A A A A A A A A A A A A A Vibrational Frequency (cm‐1) 129.9173 133.1610 165.0993 297.3117 393.3760 420.9636 651.4031 808.4592 967.1117 1031.0847 1041.1498 1067.7021 1079.4323 1268.4093 1396.3399 1407.8247 1469.6893 1471.8583 1475.1883 1479.1404 1837.0340 3027.5872 3063.0092 3115.4468 3141.9740 3144.5008 3159.5635 Intensity 0.1908 0.3820 3.4353 0.8774 2.3414 0.4517 4.9101 7.6788 0.2248 0.2897 3.8552 0.8822 7.3902 49.1785 2.3361 1.1758 4.1514 12.9128 9.0993 5.7105 5.8171 29.6473 20.1464 17.7014 13.3034 7.5294 7.5021 S29
Atom C C C C H H H C H H H Coordinates (Angstroms) X Y Z 0.777942 0.288971 ‐0.429944 ‐0.726448 0.314840 0.002155 0.014742 1.392962 0.176670 ‐1.911030 ‐0.580379 0.016939 ‐2.152172 ‐0.912421 ‐1.008732 ‐1.713176 ‐1.477014 0.630495 ‐2.782395 ‐0.047781 0.435350 1.872101 ‐0.598330 0.104694 1.893110 ‐1.565667 ‐0.428840 2.853314 ‐0.110599 ‐0.039769 1.737484 ‐0.794900 1.188407 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.088732 
1 Electronic Energy ‐193.983523 
RB3LYP/6‐31G(d) Electronic and Zero‐Point Energy ‐193.894792 (Energies in Hartrees/particle) C2V Dipole Moment (D) 5.4835 Symmetry A2 B1 B2 B1 A1 B1 B2 A1 A2 B2 A1 B1 B2 A1 B2 A1 B2 A2 B1 A1 A1 B2 A1 A2 B1 B2 A1 Vibrational Frequency (cm‐1) 75.6935 133.1333 175.8653 222.4287 365.5867 499.8673 566.9654 751.3608 930.6652 949.0079 1047.8753 1104.8350 1248.3777 1371.0037 1413.8713 1426.0330 1488.1850 1491.9514 1513.8275 1523.7228 2057.2508 3033.6550 3040.9038 3082.3351 3089.1795 3172.3408 3172.7366 Intensity 0.0000 0.0082 3.7943 7.1792 0.7465 2.8204 6.4560 1.7846 0.0000 1.4603 1.4740 5.2913 27.6289 36.0913 17.0585 4.0558 3.8686 0.0000 19.9832 8.1518 499.2432 0.2024 11.5246 0.0000 14.9015 10.1308 2.1634 S30
Atom C C C C H H H C H H H Coordinates (Angstroms) X Y Z 0.000000 0.000000 ‐0.230144 0.000000 0.000000 1.111247 0.000000 0.000000 2.393602 0.000000 1.281365 ‐1.017899 0.000000 2.155995 ‐0.366271 0.879582 1.317963 ‐1.675226 ‐0.879582 1.317963 ‐1.675226 0.000000 ‐1.281365 ‐1.017899 ‐0.879582 ‐1.317963 ‐1.675226 0.879582 ‐1.317963 ‐1.675226 0.000000 ‐2.155995 ‐0.366271 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.088634 
1 Electronic Energy ‐193.395614 
RCCSD(FC)/CC‐pVDZ Electronic and Zero‐Point Energy ‐193.306981 (Energies in Hartrees/particle) C2V Dipole Moment (D) 5.1741 Symmetry A2 B1 B2 B1 A1 B1 B2 A1 A2 B2 A1 B1 B2 A1 B2 A1 B2 A2 B1 A1 A1 B2 A1 A2 B1 B2 A1 Vibrational Frequency (cm‐1) 92.1775 141.5648 163.6066 191.6875 358.5011 474.0025 553.9198 757.5841 926.2103 955.1215 1042.1200 1092.3394 1266.6692 1370.3104 1404.6009 1407.6321 1462.4313 1467.7029 1488.8837 1497.5024 2032.6957 3055.8352 3060.6676 3126.2594 3131.4042 3191.7262 3192.5964 Intensity 0.0000 0.3651 2.7910 5.2068 0.5948 1.8209 8.5059 3.2598 0.0000 0.1673 3.7366 2.6574 18.2359 13.7415 13.8288 1.3873 4.2887 0.0000 16.7727 14.1693 539.4240 1.9848 14.7981 0.0000 14.5910 7.3124 2.5307 S31
Atom C C C C H H H C H H H Coordinates (Angstroms) X Y Z 0.000000 0.000000 ‐0.235343 0.000000 0.000000 1.115008 0.000000 0.000000 2.416909 0.000000 1.287025 ‐1.025976 0.000000 2.167720 ‐0.366994 0.889523 1.316880 ‐1.683436 ‐0.889523 1.316880 ‐1.683436 0.000000 ‐1.287025 ‐1.025976 ‐0.889523 ‐1.316880 ‐1.683436 0.889523 ‐1.316880 ‐1.683436 0.000000 ‐2.167720 ‐0.366994 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.086641 
3 Electronic Energy ‐193.926654 
UB3LYP/6‐31G(d) Electronic and Zero‐Point Energy ‐193.840013 (Energies in Hartrees/particle) CS Dipole Moment (D) 2.7674 Symmetry A A A A A A A A A A A A A A A A A A A A A A A A A A A Vibrational Frequency (cm‐1) 111.6681 130.5956 185.5836 265.4297 335.5807 448.9575 567.3079 720.0276 978.4911 984.1474 1017.0776 1066.0893 1176.1532 1213.4666 1414.6150 1421.0372 1465.8603 1498.6668 1504.2426 1512.5244 1558.3035 3017.0372 3021.5716 3062.7789 3063.2914 3140.4924 3149.9558 Intensity 0.1304 0.0309 1.2792 0.5176 0.9681 2.2796 5.4896 88.8591 0.9198 1.3223 48.9914 0.9716 1116.5035 28.2983 125.9061 3.9621 109.5575 0.0135 7.5520 15.9947 148.5521 13.4406 45.4806 4.8742 39.0525 13.6368 10.7019 S32
Atom C C C C H H H C H H H Coordinates (Angstroms) X Y Z 0.000000 ‐0.028241 ‐0.244150 0.000000 ‐0.086392 1.118357 0.000000 0.224781 2.363903 0.000000 1.286160 ‐0.983052 0.000000 2.137837 ‐0.299248 0.883020 1.363928 ‐1.633594 ‐0.883020 1.363928 ‐1.633594 0.000000 ‐1.305006 ‐1.049784 ‐0.883751 ‐1.348677 ‐1.702568 0.883751 ‐1.348677 ‐1.702568 0.000000 ‐2.194542 ‐0.414803 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.086788 
3 Electronic Energy ‐193.341923 
UCCSD(FC)/CC‐pVDZ Electronic and Zero‐Point Energy ‐193.255136 (Energies in Hartrees/particle) CS Dipole Moment (D) 1.6751 Symmetry A" A" A' A" A' A" A' A' A" A' A' A" A' A' A' A' A" A' A' A" A' A' A' A" A" A' A' Vibrational Frequency (cm‐1) 101.6202 111.7870 156.3994 267.5727 338.0105 409.3203 483.7797 728.3544 963.7831 975.5785 1016.7337 1055.5889 1233.8913 1300.6509 1406.2985 1416.8773 1469.4000 1474.9927 1478.9067 1483.4555 1605.7814 3037.7605 3041.4390 3100.5148 3101.1595 3164.1271 3171.5312 Intensity 0.4038 0.1273 15.5661 2.2955 0.0444 0.5299 87.2714 43.0725 0.3770 1.0189 13.8393 0.0182 323.9891 280.6608 1.9225 4.3654 0.0590 35.9076 77.5319 14.1580 530.0456 16.5492 39.5359 7.1955 34.8234 14.1631 12.6584 S33
Atom C C C C H H H C H H H Coordinates (Angstroms) X Y Z 0.000000 0.249685 0.000000 ‐0.257394 ‐1.114287 0.000000 ‐0.183700 ‐2.379062 0.000000 ‐1.143914 1.238276 0.000000 ‐2.122961 0.732550 0.000000 ‐1.087397 1.894538 0.890918 ‐1.087397 1.894538 ‐0.890918 1.413501 0.783796 0.000000 1.586294 1.419645 ‐0.890667 1.586294 1.419645 0.890667 2.154208 ‐0.031365 0.000000 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.085082 
3 Electronic Energy ‐193.989652 
UB3LYP/6‐31G(d) Electronic and Zero‐Point Energy ‐193.904570 (Energies in Hartrees/particle) D3 Dipole Moment (D) 0.0000 Symmetry A1 E E E E E E A1 A2 E E E E A2 A1 E E E E A1 A2 A2 A1 E E E E Vibrational Frequency (cm‐1) 7.9942 18.8358 18.8359 58.1546 58.1550 395.0866 395.0866 635.3374 1014.2409 1031.3238 1031.3239 1039.7894 1039.7894 1432.8373 1441.5583 1494.5070 1494.5071 1494.8817 1494.8817 1685.8203 1875.7878 2995.6829 2997.2765 3048.5919 3048.5919 3048.9842 3048.9842 Intensity 0.0000 9.0691 9.0692 0.0002 0.0002 1.3936 1.3936 0.0000 0.1736 3.7632 3.7633 1.7438 1.7438 39.4482 0.0000 5.9797 5.9816 4.1352 4.1369 0.0000 0.0774 128.7770 0.0000 20.8828 20.8689 15.7272 15.7401 S34
Atom C H H H C C C C H H H Coordinates (Angstroms) X Y Z 0.000000 0.000000 2.728162 0.316325 0.971352 3.136424 ‐0.999378 ‐0.211731 3.136424 0.683053 ‐0.759621 3.136424 0.000000 0.000000 1.275354 0.000000 0.000000 0.000000 0.000000 0.000000 ‐1.275354 0.000000 0.000000 ‐2.728162 ‐0.316325 0.971352 ‐3.136424 0.999378 ‐0.211731 ‐3.136424 ‐0.683053 ‐0.759621 ‐3.136424 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.084062 
3 Electronic Energy ‐194.063161 
UB3LYP/CC‐pVTZ Electronic and Zero‐Point Energy ‐193.979100 (Energies in Hartrees/particle) D3 Dipole Moment (D) 0.0000 Symmetry A1 E E E E E E A1 A2 E E E E A2 A1 E E E E A1 A2 A2 A1 E E E E Vibrational Frequency (cm‐1) 7.7194 35.2158 35.2217 67.1487 67.1510 356.7488 356.7492 630.0213 1003.8354 1016.1136 1016.1137 1024.3937 1024.3937 1406.0593 1413.0399 1463.1239 1463.1240 1463.5468 1463.5469 1673.5788 1853.4126 2979.4034 2980.5421 3024.4659 3024.4660 3024.8417 3024.8418 Intensity 0.0000 11.6719 11.6718 0.0000 0.0000 0.9770 0.9770 0.0000 0.2145 2.7696 2.7696 0.0002 0.0002 22.5681 0.0000 12.1868 12.1871 0.0013 0.0013 0.0000 0.2043 118.2291 0.0000 28.5248 28.5241 0.0034 0.0034 S35
Atom C H H H C C C C H H H Coordinates (Angstroms) X Y Z 0.000000 0.000000 2.714966 ‐0.506285 0.883115 3.118704 ‐0.511658 ‐0.880013 3.118704 1.017943 ‐0.003102 3.118704 0.000000 0.000000 1.268143 0.000000 0.000000 0.000000 0.000000 0.000000 ‐1.268143 0.000000 0.000000 ‐2.714966 ‐1.017943 ‐0.003102 ‐3.118704 0.506285 0.883115 ‐3.118704 0.511658 ‐0.880013 ‐3.118704 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.085641 
3 Electronic Energy ‐193.392913 
UCCSD(FC)/CC‐pVDZ Electronic and Zero‐Point Energy ‐193.307272 (Energies in Hartrees/particle) CS Dipole Moment (D) 0.7781 Symmetry A" A" A" A' A' A" A' A' A' A" A" A' A' A' A' A' A" A" A' A' A' A' A' A" A" A' A' Vibrational Frequency (cm‐1) 8.4082 57.7996 84.9822 103.9299 165.2611 342.8546 402.8078 657.4672 985.3963 1008.6764 1032.3170 1033.2659 1038.4864 1405.4505 1412.8620 1467.5520 1472.8505 1474.1176 1474.3931 1550.8162 1828.4330 3036.8212 3048.8184 3108.5822 3127.3690 3130.6515 3131.5965 Intensity 0.9555 4.4103 1.8496 7.0428 5.2577 0.9729 5.4047 1.9639 0.7618 0.3392 1.4514 1.1714 10.5321 15.8024 7.9762 5.7959 3.7931 7.1233 6.2393 4.6243 6.7685 43.2529 36.3668 14.3211 11.4654 8.5219 14.4880 S36
Atom C H H H C C C C H H H Coordinates (Angstroms) X Y Z 2.703019 0.025478 0.000000 2.938157 ‐0.580689 0.896189 2.938157 ‐0.580689 ‐0.896189 3.373191 0.903293 0.000000 1.280239 0.445056 0.000000 0.000000 0.116538 0.000000 ‐1.262457 ‐0.045443 0.000000 ‐2.712050 ‐0.309544 0.000000 ‐3.010344 ‐0.886050 0.894794 ‐3.281327 0.637682 0.000000 ‐3.010344 ‐0.886050 ‐0.894794 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.085007 
3 Electronic Energy ‐193.626328 
UCCSD(T)(FC)/ANO1 Electronic and Zero‐Point Energy ‐193.541321 (Energies in Hartrees/particle) C1 Dipole Moment (D) 0.6259 Symmetry A A A A A A A A A A A A A A A A A A A A A A A A A A A Vibrational Frequency (cm‐1) 9.4673 37.5705 71.5812 82.1986 148.3906 348.0392 383.5912 642.3394 978.6456 1009.5176 1027.2957 1030.7878 1035.3375 1401.7762 1408.6847 1471.5206 1475.1011 1476.7919 1477.7339 1589.8829 1818.2390 3012.5624 3021.3735 3075.4154 3089.8036 3092.7559 3097.3417 Intensity 0.9088 5.5747 1.8399 10.3381 4.1848 0.3184 6.2452 1.4009 1.6523 1.1293 0.9778 1.3762 7.4619 12.1330 2.4353 7.4812 7.2444 6.5978 5.8317 2.0457 7.2450 32.9428 28.1727 10.2464 7.7871 7.4066 9.0291 S37
Atom C C C C C H H H H H H Coordinates (Angstroms) X Y Z 0.000000 0.000000 0.000000 0.000000 0.000000 1.262484 0.113485 0.000000 ‐1.291096 ‐0.003160 0.021772 2.722275 ‐0.399848 ‐0.027389 ‐2.665392 0.863055 ‐0.512085 3.121940 0.414088 0.035787 ‐3.390555 ‐0.903047 ‐0.455893 3.118341 ‐0.950152 ‐0.953053 ‐2.860949 0.028656 1.046638 3.101752 ‐1.076823 0.812899 ‐2.848648 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.084026 
3 Electronic Energy ‐193.626001 
UCCSD(T)(FC)/ANO1 Electronic and Zero‐Point Energy ‐193.541975 (Energies in Hartrees/particle) D3 Dipole Moment (D) 0.0000 Symmetry Vibrational Frequency (cm‐1) E ‐90.6308 E ‐90.6308 E ‐60.4582 E ‐60.4582 A1 ‐5.7698 E 322.9421 E 322.9421 A1 623.1544 A2 988.0381 E 1019.0663 E 1019.0663 E 1026.4840 E 1026.4840 A2 1404.5383 A1 1410.5840 E 1474.4125 E 1474.4125 E 1474.8931 E 1474.8931 A1 1667.0913 A2 1793.5472 A2 3014.4718 A1 3015.0384 E 3082.6704 E 3082.6704 E 3082.9246 E 3082.9246 Intensity 0.0003 0.0003 10.9521 10.9521 0.0000 0.0905 0.0905 0.0000 0.1819 0.3578 0.3578 1.2665 1.2665 19.2961 0.0000 2.3825 2.3825 10.4993 10.4993 0.0000 2.2948 71.2187 0.0000 3.1334 3.1334 14.3872 14.3872 S38
Atom C C C H H H C C H H H Coordinates (Angstroms) X Y Z 0.000000 0.000000 1.000000 1.459628 0.000000 1.000000 2.734818 0.000000 1.000000 ‐0.394010 0.000000 ‐0.020289 ‐0.394010 ‐0.883596 1.510145 ‐0.394010 0.883596 1.510145 4.010008 0.000000 1.000000 5.469637 0.000000 1.000000 5.863646 0.349499 0.041438 5.863646 0.655390 1.781955 5.863646 ‐1.004888 1.176607 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.0844310 
3 Electronic Energy ‐193.626003 
UCCSD(T)(FC)/ANO1 Electronic and Zero‐Point Energy ‐193.541572 (Energies in Hartrees/particle) D3d Dipole Moment (D) 0.0000 Symmetry Vibrational Frequency (cm‐1) A1u ‐166.1777 Eg ‐141.0033 Eg ‐141.0033 Eu ‐107.5785 Eu ‐107.5785 Eu 299.1842 Eu 299.1842 A1g 633.7504 A2u 1006.3549 Eu 1011.6308 Eu 1011.6308 Eg 1017.5097 Eg 1017.5097 A2u 1400.3592 A1g 1405.8032 Eu 1470.9467 Eu 1470.9467 Eg 1471.3445 Eg 1471.3445 A1g 1694.5182 A2u 1840.6885 A2u 3042.7846 A1g 3043.3684 Eu 3112.8905 Eg 3112.8905 Eg 3113.1484 Eg 3113.1484 Intensity 0.0000 0.0000 0.0000 11.0121 11.0121 0.0313 0.0313 0.0000 0.0507 1.8534 1.8534 0.0000 0.0000 18.1150 18.1150 13.0963 13.0963 0.0000 0.0000 0.0000 2.4599 71.837 0.0000 7.4065 7.4065 0.0000 0.0000 S39
Atom C C C C C H H H H H H Coordinates (Angstroms) X Y Z 0.000000 0.000000 1.000000 1.269300 0.000000 1.000000 ‐1.269300 0.000000 1.000000 2.723010 0.000000 1.000000 ‐2.723010 0.000000 1.000000 3.115071 0.000000 ‐0.017424 ‐3.115071 0.000000 2.017424 3.115071 0.881115 1.508712 ‐3.115071 ‐0.881115 0.491288 3.115071 ‐0.881115 1.508712 ‐3.115071 0.881115 0.491288 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.084026 
3 Electronic Energy ‐193.626000 
UCCSD(T)(FC)/ANO1 Electronic and Zero‐Point Energy ‐193.541975 (Energies in Hartrees/particle) D3h Dipole Moment (D) 0.0000 Symmetry Vibrational Frequency (cm‐1) E '' ‐90.8817 E '' ‐90.8817 E '' ‐60.2618 E '' ‐60.2618 A ''1 ‐ 6.4558 E ' 322.9470 E ' 322.9470 A ''1 623.1684 A ''2 988.0586 E '' 1018.7998 E '' 1018.7998 E ' 1026.7567 E ' 1026.7567 A ''2 1404.5367 A '1 1410.5953 E '' 1474.4046 E '' 1474.4046 E ' 1474.9101 E ' 1474.9101 A '1 1667.1149 A ''2 1793.4496 A ''2 3014.4456 A '1 3015.0150 E '' 3082.6218 E '' 3082.6218 E ' 3082.9046 E ' 3082.9046 Intensity 0.0000 0.0000 10.9569 10.9569 0.0000 0.0915 0.0915 0.0000 0.1821 0.0000 0.0000 1.5514 1.5514 19.2928 0.0000 0.0000 0.0000 12.8744 12.8744 0.0000 2.2979 71.2399 0.0000 0.0000 0.0000 17.4794 17.4794 S40
Atom C C C C C H H H H H H Coordinates (Angstroms) X Y Z 0.000000 0.000000 1.000000 1.275186 0.000000 1.000000 ‐1.275186 0.000000 1.000000 2.734807 0.000000 1.000000 ‐2.734807 0.000000 1.000000 3.128823 0.000000 ‐0.020290 ‐3.128823 0.000000 ‐0.020290 3.128823 0.883597 1.510145 ‐3.128823 ‐0.883597 1.510145 3.128823 0.883597 1.510145 ‐3.128823 ‐0.883597 1.510145 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.086484 
1 Electronic Energy ‐193.970752 
RB3LYP/6‐31G(d) Electronic and Zero‐Point Energy ‐193.884268 (Energies in Hartrees/particle) C1 Dipole Moment (D) 2.5042 Symmetry A A A A A A A A A A A A A A A A A A A A A A A A A A A Vibrational Frequency (cm‐1) 43.2891 90.7129 124.4260 183.4648 211.8135 448.3570 521.7325 720.1603 836.7996 1022.8032 1045.2086 1070.0129 1091.5702 1365.3904 1382.5335 1426.5650 1456.7891 1477.9767 1514.6630 1528.3618 2120.1962 2982.5134 3017.1170 3033.9511 3075.6159 3078.1861 3091.8197 Intensity 7.2650 8.9726 2.6514 6.3249 4.4681 2.7252 3.0568 8.9854 10.3359 18.4035 10.2022 1.0882 7.7699 23.7620 15.3859 9.5894 6.1714 11.1979 31.8209 11.0039 51.5680 17.3108 33.3321 54.1128 20.2818 17.1482 18.0672 S41
Atom C H H H C C C H C H H Coordinates (Angstroms) X Y Z 2.588444 0.178356 0.005027 3.125113 ‐0.542801 0.636320 2.872557 1.195304 0.306870 2.956309 0.027844 ‐1.020287 1.156883 ‐0.049536 0.010380 ‐0.063535 ‐0.264475 ‐0.001271 ‐1.360075 ‐0.654360 ‐0.015377 ‐2.735310 0.443892 1.048496 ‐2.438613 0.369396 ‐0.013618 ‐2.179993 1.385224 ‐0.350366 ‐3.337291 0.014255 ‐0.531875 Charge Multiplicity Theory/Basis Set Full Point Group 0 Zero‐point Energy 0.086738 
1 Electronic Energy ‐193.375289 
RCCSD(FC)/CC‐pVDZ Electronic and Zero‐Point Energy ‐193.288551 (Energies in Hartrees/particle) C1 Dipole Moment (D) 2.7602 Symmetry A A A A A A A A A A A A A A A A A A A A A A A A A A A Vibrational Frequency (cm‐1) 31.6080 125.6969 131.1732 207.3563 218.9362 421.9407 533.1063 721.8094 773.8905 1031.0836 1042.1137 1062.9355 1085.0674 1280.5419 1353.5348 1409.4331 1421.5986 1462.4204 1487.9676 1499.1544 2167.5511 3010.4981 3062.8779 3086.8546 3145.6151 3147.3783 3151.3769 Intensity 3.1421 7.1592 0.4605 2.2007 4.1135 1.5196 0.2084 0.8623 19.4477 5.3408 7.1912 0.3792 6.5573 56.4496 20.5361 14.3958 2.6852 8.6390 13.6238 7.4239 96.1938 5.0094 20.0772 35.6007 9.8211 15.3220 8.5046 S42
Atom C H H H C C C C H H H Coordinates (Angstroms) X Y Z ‐2.593844 0.192984 ‐0.001391 ‐3.153502 ‐0.622382 ‐0.491697 ‐2.842269 1.151726 ‐0.488254 ‐2.931236 0.247616 1.049739 ‐1.146341 ‐0.068752 ‐0.010067 0.073778 ‐0.302918 ‐0.003716 1.411261 ‐0.712419 ‐0.013658 2.404223 0.417320 ‐0.013964 3.363627 0.119746 ‐0.469918 2.056150 1.389632 ‐0.414699 2.612777 0.556376 1.071605