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SUPPLEMENTARY MATERIAL

(Tables S1–S3)

Theoretical Study of Reaction of Trifluoromethyl Radical

with Hydroxyl and Hydrogen Radicals

Haruhiko Fukaya, Taizo Ono, and Takashi Abe

Chemistry Department, National Industrial Research Institute of Nagoya

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TABLE S1.

The electronic energies calculated by ab initio methods.a

Species HF MP2 QCISD

BS1 BS2 BS3 BS1 BS2 BS3 BS1 BS2

CF₃· -336.13118 -336.23471 -336.26027 -336.74407 -337.02188 -337.14067 -336.75585 -337.02599

H · -0.49823 -0.49981 -0.49982 -0.49823 -0.49981 -0.49982 -0.49823 -0.49981

CF₃H -336.77338 -336.87795 -336.90240 -337.41491 -337.69679 -337.81813 -337.42842 -337.70239

OH· -75.38833 -75.41319 -75.41918 -75.53209 -75.59076 -75.62012 -75.54689 -75.60432

CF₃OH -411.65485 -411.78087 -411.81141 -412.47020 -412.80740 -412.95858 -412.48348 -412.81049

H₂ -1.13133 -1.13300 -1.13303 -1.15766 -1.16276 -1.16466 -1.16516 -1.17082

H₂O -76.02361 -76.05111 -76.05916 -76.21979 -76.28648 -76.32326 -76.22895 -76.29298

F₂C=O -311.61531 -311.71227 -311.73558 -312.25271 -312.50123 -312.61374 -312.25816 -312.49890

HF -100.01169 -100.04996 -100.05774 -100.19464 -100.29292 -100.33213 -100.19938 -100.29526

CF₂: -236.66074 -236.73404 -236.75210 -237.11157 -237.30417 -237.38748 -237.12704 -237.31377

F · -99.36496 -99.39753 -99.40181 -99.48727 -99.57314 -99.60212 -99.49795 -99.58366

TS3 -337.22783 -337.33454 -337.35937 -337.87707 -338.16325 -338.28471 -337.89590 -338.17532

TS4 -412.10947 -412.24031 -412.27081 -412.92555 -413.26932 -413.42097 -412.95394 -413.28860

TS5 -412.05252 -412.18080 -412.21338 -412.88544 -413.22817 -413.38407 -412.90780 -413.23995

TS7 -336.61986 -336.72898 -336.75588 -337.28326 -337.56908 -337.69329 -337.29619 -337.57292

TS8 -411.55568 -411.68208 -411.71287 -412.39568 -412.73298 -412.88479 -412.40257 -412.72886 a

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TABLE S2.

The electronic energies calculated by the DFT methods.a

Species BVWN BLYP B3LYP

BS1 BS2 BS3 BS1 BS2 BS3 BS1 BS2 BS3

CF₃· -339.30104 -339.42118 -339.44541 -337.51828 -337.64174 -337.66877 -337.55102 -337.66760 -337.69319

H · -0.53574 -0.53748 -0.53756 -0.49545 -0.49755 -0.49772 -0.50027 -0.50216 -0.50226

CF₃H -340.01300 -340.13508 -340.15948 -338.18532 -338.31053 -338.33788 -338.22740 -338.34556 -338.37098

OH· -76.18879 -76.21844 -76.22752 -75.71226 -75.74235 -75.75333 -75.72848 -75.75686 -75.76603

CF₃OH -415.66266 -415.80919 -415.83868 -413.41221 -413.56232 -413.59501 -413.46301 -413.60477 -413.63551

H₂ -1.26038 -1.26182 -1.26182 -1.16791 -1.16960 -1.16960 -1.17854 -1.18001 -1.18001

H₂O -76.91887 -76.95259 -76.96446 -76.39888 -76.43331 -76.44734 -76.41974 -76.45212 -76.46420

F₂C=O -314.69819 -314.80877 -314.83022 -312.97864 -313.09161 -313.11543 -313.00795 -313.11529 -313.13804

HF -100.95377 -101.00154 -101.01459 -100.41148 -100.46083 -100.47642 -100.42746 -100.47357 -100.48660

CF₂: -238.96304 -239.04788 -239.06437 -237.66823 -237.75599 -237.77466 -237.68975 -237.77278 -237.79055

F · -100.20059 -100.24050 -100.24827 -99.70214 -99.74344 -99.75312 -99.71553 -99.75374 -99.76168

TS3 -340.54064 -340.66296 -340.68668 -338.67338 -338.79880 -338.82528 -338.71471 -338.83338 -338.85836

TS4 -416.20303 -416.35426 -416.38552 —b

—b

-413.95384 -414.10040 -414.13292

TS5 -416.15579 -416.30453 -416.33567 -413.86611 -414.01890 -414.05357 -413.91011 -414.05456 -414.08767

TS7 -339.90747 -340.03270 -340.05960 -338.07929 -338.20788 -338.23797 -338.10715 -338.22884 -338.25679

TS8 -415.60251 -415.74883 -415.77782 -413.35382 -413.50350 -413.53553 -413.39394 -413.53538 -413.56565 a

The energies are given in hartree. b

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TABLE S3.

The thermal energy corrections at 298.15 K.a

Species HF MP2 QCISD BVWN BLYP B3LYP

BS1 BS2 BS3 BS1 BS2 BS3 BS1 BS2 BS1 BS2 BS3 BS1 BS2 BS3 BS1 BS2 BS3

CF₃· 16.90 16.83 16.87 15.87 15.76 —b

15.91 15.86 14.90 14.71 14.68 14.98 14.78 14.72 15.62 15.44 15.41

CF₃H 31.34 31.10 31.03 29.63 29.33 —b

29.68 29.42 28.01 27.70 27.55 27.88 27.56 27.38 28.94 28.62 28.48

OH· 11.60 11.61 11.61 11.12 11.09 11.12 10.97 10.97 10.54 10.58 10.62 10.42 10.46 10.50 10.78 10.80 10.84

CF₃OH 36.34 36.24 36.18 34.07 33.86 —b

34.30 —b

32.25 32.02 31.87 32.21 31.97 31.76 33.47 33.25 33.08

H₂ 12.92 12.82 12.81 12.86 12.68 12.67 12.63 12.41 12.61 12.52 12.51 12.37 12.27 12.26 12.54 12.44 12.43

H₂O 26.03 25.99 25.95 24.71 24.59 24.47 24.71 24.64 23.69 23.73 23.75 23.42 23.46 23.48 24.20 24.21 24.20

F₂C=O 18.97 18.92 18.93 17.45 17.37 —b

17.61 17.60 16.69 16.56 16.51 16.73 16.59 16.51 17.43 17.30 17.26

HF 12.60 12.62 12.59 11.92 11.94 11.88 11.91 11.98 11.41 11.47 11.45 11.29 11.37 11.35 11.67 11.73 11.70

CF₂: 10.73 10.70 10.72 10.10 10.02 10.02 10.04 10.02 9.45 9.35 9.32 9.51 9.41 9.36 9.95 9.86 9.83

TS3 28.32 28.01 28.06 27.62 27.26 —b

27.36 27.04 26.12 25.74 25.73 26.09 25.75 25.71 27.00 26.68 26.64

TS4 38.82 38.77 38.81 37.24 36.95 —b

36.92 —b

36.35 35.67 34.85 —c

—c

36.29 36.14 36.11

TS5 37.66 37.57 37.66 36.34 36.10 —b

35.92 —b

33.88 33.65 33.58 33.86 33.58 33.45 35.23 34.98 34.89

TS7 24.43 24.39 24.50 22.88 22.71 22.77 22.91 22.80 21.78 21.52 21.67 21.64 21.38 21.50 22.48 22.28 22.35

TS8 29.97 29.79 29.72 28.25 27.99 —b

28.36 28.19 26.83 26.58 26.45 26.87 26.59 26.40 27.89 27.60 27.44 a

The energies are given in millihartree. b

Could not calculate. c