(4C)

N1

O2

O3 O4

O5

O6H14

H13

H7H8

H9

H10H11

H12

(4F)

N1

O2

O3

O4

O5

O6

H13

H14

H7 H8

H9

H10

H11

H12

Supplementary Figure1. Calculated structures of isomers by MP2/aug-cc-pVTZ level of theory. Toshio et al.

(4B)

N1

O2

O4O3

O5

O6H7

H8

H9

H10

H11

H12

H13

H14

(4E)

N1

O2

O3

O4

O5

O6

H14H13

H7

H8

H9H10

H11

H12

(4I)

N1

O2

O4

O3

O5O6

H13

H7H8

H9

H10

H11

H12

H14

(4K)

N1

O2

O4O3

O5O6

H7

H8

H9

H10

H11

H12

H13

H14

Supplementary Figure1(continue). Toshio et al.

(4M)

N1

O2

O4O3

O5

O6H7 H8

H9H10

H11

H12

H13H14

(4N)

N1O2

O4

O3

O5

O6

H7H8

H9

H10

H11 H12

H13

H14

(4P)

N1

O2

O4

O3

O5

O6

H8

H9

H10

H11 H12

H13

H14

H7

(4O)

N1

O2

O4

O3O5

O6

H7H8

H9

H10

H11H12

H13H14

Supplementary Figure1(continue). Toshio et al.

(4Q)N1

O2

O4

O3

O5

O6

H8 H9

H10

H11

H12H13

H14

H7

(5B)

N1

O2

O3

O4O5

O6

O7

H8

H9

H10

H11H12

H13H14

H15H16

H17

(5E)N1

O2

O3

O4

O5

O6

O7

H14

H8H9

H10

H11H12

H13

H15

H16H17

Supplementary Figure1(continue). Toshio et al.

(5G) N1

O2

O3

O4

O5

O6O7

H15

H16

H17

H14

H8

H9

H10

H11

H12H13

(5L)N1O2

O3

O4O5

O6

O7

H8H9

H10

H11H12

H13

H14

H15

H16H17

(5I)N1

O2 O3

O4

O5

O6

O7

H9

H10H11

H12H13

H8

H14

H15

H16

H17

Supplementary Figure1(continue). Toshio et al.

(5H) N1O2 O3

O4

O5O6

O7

H8

H9H10

H11

H12

H13

H14H15

H16

H17

(5K)

N1

O2

O7O3O4

O5

O6

H8H9H10

H11 H12

H13

H14H15

H16H17

(5P) N1O2

O4

O3

O5

O6

O7H9

H10

H11H12

H13H15

H8

H16

H17

H14

Supplementary Figure1(continue). Toshio et al.

moleculeMP2/aug-cc-pVTZ//B3LYP/aug-cc-pVDZ

MP2/aug-cc-pVTZ

E (hartree) Ea E (hartree) ZPEa Ea E+ZPEa

n=44B -434.80024 -0.85 -434.80198 60.34 -0.45 0.57 4C -434.79990 -0.63 -434.80131 60.12 -0.03 0.77 4E -434.79766 0.77 -434.79877 59.88 1.57 2.12 4F not available -434.79803 59.50 2.03 2.20 4I not available -434.79711 59.84 2.61 3.12 4K not available -434.79556 59.66 3.58 3.92 4M not available -434.79341 59.32 4.93 4.92 4Nb -434.79065 58.67 6.66 6.00 4O -434.79228 4.15 -434.79427 61.07 4.39 6.13 4P -434.79127 4.78 -434.79264 60.88 5.42 6.96 4Q -434.79116 4.85 -434.79161 60.78 6.06 7.51

n=55B not available -511.14870 73.57 2.37 0.33 5E -511.14896 -0.24 -511.15018 75.26 1.44 1.09 5G -511.14811 0.29 -511.14871 74.45 2.37 1.20 5H -511.14925 -0.42 -511.14976 75.21 1.71 1.31 5I -511.14926 -0.43 -511.14869 74.63 2.38 1.40 5K -511.14346 3.21 -511.14636 74.09 3.84 2.32 5L not available -511.14741 74.90 3.18 2.47 5Pb -511.13901 72.50 8.45 5.34 a Values are given in kcal/mol.b Transition state.

Toshio et al.

Supplementary Table1. Calculated electronic energies (E), zero point energies (ZPE), relative energies (E), and ZPE corrected relative energies (E+ZPE) at the MP2/aug-cc-pVTZ//B3LYP/aug-cc-pVDZ and the MP2/aug-cc-pVTZ levels of theory

isomer atomcoordinate / Å

isomer atomcoordinate / Å

X Y Z X Y Z4A N1 -0.92511 0.00641 -0.07897 4D N1 -2.89448 -0.25799 0.21134

O2 -1.13057 0.01013 0.9864 O2 -2.96153 0.21404 -0.80789O3 0.816 -1.5971 0.0703 O3 -1.31587 -0.09024 0.84097O4 0.8271 1.59935 0.06316 O4 0.87417 0.00612 -0.37776O5 3.15165 -0.00784 -0.27862 O5 2.32144 -2.09773 -0.06162O6 -3.43838 -0.00505 -0.44062 O6 2.17748 2.18278 0.05414H7 0.85691 -2.52261 -0.19382 H7 -1.40927 -0.55125 1.69033H8 1.70329 -1.23866 -0.10173 H8 -0.0156 -0.0714 0.14208H9 0.87482 2.52331 -0.20519 H9 1.35226 0.86922 -0.18014H10 1.71145 1.23342 -0.10803 H10 1.47263 -0.78889 -0.22904H11 3.80505 -0.008 0.43178 H11 3.04049 -2.21904 0.56808H12 3.67243 -0.0117 -1.09098 H12 2.52877 -2.66445 -0.8131H13 -3.97468 -0.76675 -0.68806 H13 2.11074 2.74477 0.83391H14 -3.97988 0.7503 -0.69615 H14 2.41579 2.76719 -0.67428

4B N1 -2.18052 -0.00049 -0.74997 4E N1 -1.07883 1.43187 0.33716O2 -2.92614 -0.00054 0.04697 O2 -2.10444 1.66766 -0.01572O3 -0.78758 -1.55049 0.1037 O3 -0.48518 -0.14629 -0.48623O4 1.35143 0.00086 0.85126 O4 1.63782 -0.63582 0.81063O5 -0.78844 1.55069 0.10311 O5 -2.77373 -1.44454 -0.14953O6 3.65709 -0.00047 -0.56168 O6 3.90746 0.1223 -0.43371H7 -0.59165 -2.40919 -0.28873 H7 -1.22861 -0.7913 -0.34366H8 0.07743 -1.16198 0.35191 H8 0.3508 -0.42711 0.03429H9 1.57549 0.00168 1.78894 H9 1.81164 -1.41491 1.34777H10 2.21254 0.00063 0.37494 H10 2.4872 -0.40656 0.37198H11 -0.59317 2.40955 -0.2893 H11 -3.23362 -1.76106 -0.93624H12 0.07688 1.16276 0.35117 H12 -3.02623 -2.05924 0.54919H13 4.22869 -0.76477 -0.68999 H13 4.33931 -0.31812 -1.17286H14 4.22661 0.76435 -0.69598 H14 4.59587 0.64869 -0.0141

4C N1 0.20112 -1.51639 0.36952 4F N1 -0.73629 0.4578 -0.05719O2 0.41705 -2.12613 -0.51418 O2 -0.59024 -0.22623 -0.88703O3 -0.67001 0.20272 -0.48246 O3 1.45661 1.59157 -0.15474O4 1.25523 2.25015 -0.13912 O4 0.74576 -0.44735 1.61729O5 2.25155 -0.35657 0.39719 O5 1.87052 -1.16892 -0.76537O6 -3.25577 0.3327 0.28748 O6 -3.16729 -0.10523 -0.03741H7 -1.58977 0.36046 -0.16783 H7 1.75074 2.49661 -0.31097H8 -0.1558 1.01168 -0.30196 H8 1.60373 1.42602 0.78731H9 1.23435 2.96779 0.50551 H9 0.68986 -0.79795 2.51293H10 1.51796 2.67138 -0.967 H10 1.33318 -1.03937 1.11826H11 2.15109 0.60457 0.30108 H11 2.39033 -1.85417 -1.20031H12 3.05275 -0.48457 0.91692 H12 2.34543 -0.34149 -0.9213H13 -3.65461 0.63291 1.11101 H13 -3.5982 -0.70308 0.58413H14 -3.94816 0.4276 -0.37566 H14 -3.88397 0.45809 -0.35158

Suplementary Table2. Cartesian Coordinates of all isomers.

isomer atomcoordinate / Å

isomer atomcoordinate / Å

X Y Z X Y Z4G N1 2.78768 -0.34202 -0.03925 4J N1 2.33581 -0.70929 -0.15532

O2 2.6373 0.21981 0.92602 O2 2.34888 -0.00332 0.69967O3 1.29981 -0.84883 -0.668 O3 0.7045 -1.64694 -0.11206O4 -1.07896 -0.01296 -0.66516 O4 -1.02611 0.00159 -0.57155O5 -1.25633 2.45356 0.0419 O5 0.5689 2.20561 -0.11611O6 -2.73247 -1.5669 0.53762 O6 -3.5194 -0.22756 0.36708H7 1.59183 -1.28321 -1.48635 H7 0.75123 -2.27285 -0.85356H8 -0.09842 -0.32237 -0.64465 H8 -0.10708 -0.93044 -0.31509H9 -1.68916 -0.64412 -0.17116 H9 -1.93204 -0.09935 -0.1967H10 -1.18401 0.93778 -0.35074 H10 -0.69428 0.89593 -0.36897H11 -1.61084 2.78061 0.8763 H11 0.44821 2.81378 0.62317H12 -1.48992 3.11482 -0.61982 H12 0.68145 2.78411 -0.88037H13 -3.45993 -1.96218 0.04384 H13 -3.8329 -0.66345 1.16612H14 -2.52808 -2.18469 1.24825 H14 -4.27939 -0.19777 -0.22363

4H N1 1.65965 0.04177 -1.16556 4K N1 1.98811 -0.57069 0.39936O2 0.83984 -2.58436 -0.86435 O2 1.38774 -0.52058 1.31366O3 -1.88995 -0.77052 -0.28976 O3 1.49942 1.85752 -0.39761O4 -0.91817 1.81139 -0.26731 O4 0.73419 -1.58581 -0.90907O5 1.68785 0.8539 -0.63593 O5 -0.91714 0.21503 -0.06613O6 0.59316 -1.67037 -0.68065 O6 -3.62196 0.10561 0.17013H7 -2.78259 -1.08655 -0.46593 H7 1.83392 2.07426 -1.27631H8 -1.87916 0.17358 -0.52446 H8 1.6474 2.66653 0.10768H9 -1.35832 2.66361 -0.36017 H9 -0.03973 -0.96346 -0.8329H10 -0.074 1.89546 -0.73442 H10 0.95841 -1.6857 -1.84345H11 2.54915 1.25403 -0.80643 H11 -1.89425 0.18255 0.01551H12 1.65965 0.04177 -1.16556 H12 -0.6901 1.11543 -0.32652H13 0.83984 -2.58436 -0.86435 H13 -4.25901 -0.129 -0.51221H14 -0.37837 -1.60874 -0.792 H14 -4.13145 0.16004 0.9849

4I N1 -1.76378 -0.57351 -0.68662 4L N1 2.33072 -0.68918 -0.17193O2 -0.91173 -0.37741 -1.33878 O2 2.34945 -0.00563 0.69892O3 -1.95507 1.55922 0.1576 O3 0.70494 -1.67077 -0.0992O4 -0.8252 -0.7238 1.37624 O4 -1.03508 -0.0051 -0.54802O5 1.36118 -1.09888 -0.10052 O5 0.61922 2.18655 -0.12052O6 3.1407 0.95415 -0.02242 O6 -3.55611 -0.19266 0.35138H7 -2.62963 2.24743 0.19243 H7 0.73667 -2.29747 -0.84043H8 -1.70673 1.38229 1.07473 H8 -0.09626 -0.97082 -0.29066H9 -1.09235 -1.31796 2.08731 H9 -1.94783 -0.08908 -0.18959H10 0.09312 -0.96622 1.12586 H10 -0.70158 0.88887 -0.35562H11 1.85302 -1.92225 -0.19235 H11 0.7265 2.75468 -0.89329H12 2.04742 -0.39648 -0.07339 H12 0.50509 2.80571 0.61067H13 3.60839 1.23789 0.77021 H13 -3.88992 -0.60959 1.15225H14 3.69413 1.24361 -0.75547 H14 -4.30705 -0.15713 -0.25037

Suplementary Table2. (continue)

isomer atomcoordinate / Å

isomer atomcoordinate / Å

X Y Z X Y Z4M N1 3.16765 0.49083 -0.53784 4P N1 2.47867 0.00002 0.04303

O2 3.18495 1.16786 0.35769 O2 2.26212 0 -1.0601O3 1.98237 -0.74638 -0.33297 O3 0.99218 0.00002 0.9412O4 -0.15501 -0.71088 0.91986 O4 -0.9105 1.75788 0.0695O5 -2.17823 -0.81164 -0.43711 O5 -2.55733 -0.00008 -0.47219O6 -4.00049 1.06607 -0.0461 O6 -0.91038 -1.75785 0.06951H7 2.06907 -1.23172 -1.16905 H7 1.35896 -0.00002 1.8423H8 0.72926 -0.73526 0.35253 H8 -0.15469 1.32717 0.52391H9 -0.11275 -1.36931 1.62561 H9 -1.02805 2.64277 0.43133H10 -1.05546 -0.80441 0.34511 H10 -1.97594 0.83475 -0.21874H11 -2.60556 -1.63746 -0.68635 H11 -3.40133 -0.00011 -0.00009H12 -2.88765 -0.14069 -0.27558 H12 -1.97581 -0.83485 -0.2187H13 -4.29806 1.65005 -0.75169 H13 -1.02794 -2.64266 0.43152H14 -4.68117 1.11277 0.6333 H14 -0.15461 -1.32701 0.52388

4N N1 -2.23952 0.4144 -0.15004 4Q N1 1.79642 -1.24037 0.06817O2 -1.55389 0.94985 -0.84779 O2 0.61867 -1.18465 0.05939O3 -1.27625 -0.70422 0.8979 O3 2.3424 0.07723 0.0262O4 0.35151 -1.9466 -0.35486 O4 0.31241 2.05604 -0.13798O5 2.36291 -0.44312 -0.08956 O5 -1.92097 1.09501 0.18521O6 1.17231 2.00569 0.30638 O6 -2.29963 -1.37085 -0.12009H7 -1.95659 -1.20044 1.38239 H7 3.30397 -0.07176 0.04486H8 -0.48164 -1.41221 0.29195 H8 1.10027 1.48412 -0.13928H9 0.51956 -2.86027 -0.09123 H9 0.43713 2.73557 -0.81056H10 1.22053 -1.41339 -0.28474 H10 -0.93925 1.46964 0.02283H11 3.17764 -0.46318 -0.60146 H11 -2.23835 1.33787 1.06642H12 2.08977 0.49227 -0.00342 H12 -2.03231 0.08432 0.03913H13 1.437 2.79896 -0.17463 H13 -3.04108 -1.71978 -0.62806H14 1.21766 2.26461 1.23484 H14 -1.5884 -2.0196 -0.17438

4O N1 -2.51408 0.00002 0.07796O2 -2.36725 -0.00001 -1.03662O3 -0.97566 -0.00001 0.88225O4 0.94959 -1.78147 0.07167O5 2.61006 -0.00002 -0.34231O6 0.94961 1.78149 0.07167H7 -1.29144 -0.00002 1.80273H8 0.17656 -1.333 0.47896H9 1.12413 -2.59006 0.56676H10 1.99222 -0.83725 -0.18698H11 2.97336 -0.00002 -1.23921H12 1.99227 0.83722 -0.18698H13 1.12414 2.5901 0.56673H14 0.17657 1.33305 0.47896

Suplementary Table2. (continue)

isomer atomcoordinate / Å

isomer atomcoordinate / Å

X Y Z X Y Z5A N1 0.19987 -1.75954 0.00051 5C N1 3.11212 -0.04626 0.53051

O2 -0.40954 -1.3939 -0.82579 O2 2.58695 -0.09145 1.52769O3 -0.28914 -0.16339 1.76262 O3 1.96714 0.03072 -0.72713O4 1.3396 1.65589 0.54797 O4 -0.16601 -1.75484 -0.62611O5 -0.51592 1.30279 -1.36151 O5 -1.91976 0.06316 -0.73941O6 -2.47932 0.05938 0.08335 O6 -0.13523 1.83689 -0.46179O7 2.15164 -0.75571 -0.50252 O7 -3.80485 -0.10176 1.01082H8 -0.15064 -0.4101 2.6846 H8 2.57318 0.06324 -1.48761H9 0.32639 0.57927 1.58839 H9 0.69481 -1.31077 -0.75955H10 1.73531 2.50151 0.78522 H10 -0.15313 -2.57024 -1.13869H11 0.70936 1.82406 -0.18489 H11 -1.31149 -0.75704 -0.70864H12 -0.63839 1.76339 -2.19853 H12 -2.62345 0.03101 -0.02363H13 -1.40739 1.13706 -1.00392 H13 -1.3007 0.86743 -0.6345H14 -3.43517 0.12732 0.18249 H14 -0.102 2.68944 -0.90885H15 -2.1049 0.1367 0.9745 H15 0.71673 1.38662 -0.62913H16 3.0275 -1.12663 -0.3444 H16 -4.73044 -0.03499 0.7521H17 2.16036 0.14367 -0.11997 H17 -3.77428 0.09738 1.95242

5B N1 0.19291 -0.13367 0.06833 5D N1 -2.08176 -0.00588 -0.1121O2 0.25922 -0.18174 1.15 O2 -1.872 0.02881 0.95666O3 2.38553 -1.03483 -0.20195 O3 -0.86412 -1.8225 -0.71269O4 4.44671 0.773 -0.29599 O4 1.79739 1.44469 -0.29215O5 -1.4441 1.66994 0.17196 O5 0.72728 -0.10287 1.72787O6 -3.88711 0.31499 -0.45193 O6 1.8379 -1.34447 -0.53214O7 -1.75857 -1.5345 -0.00342 O7 -0.89684 1.80679 -0.81115H8 2.62352 -1.84033 -0.67197 H8 -1.14381 -2.36363 -1.45966H9 3.16411 -0.44839 -0.29314 H9 0.1067 -1.73066 -0.79755H10 4.8109 1.18186 -1.08804 H10 2.45216 2.15216 -0.28773H11 5.18416 0.72984 0.3219 H11 1.62515 1.21851 0.63985H12 -1.40077 2.61724 0.00548 H12 0.90008 -0.20209 2.67104H13 -2.34321 1.40535 -0.08243 H13 1.18965 -0.84253 1.30042H14 -4.59937 0.3428 0.1985 H14 2.1061 -0.43886 -0.76433H15 -4.32913 0.40913 -1.30427 H15 2.55015 -1.92511 -0.82183H16 -1.89113 -2.44525 -0.28647 H16 -1.13152 2.29802 -1.60617H17 -2.58294 -1.07147 -0.22725 H17 0.08084 1.79171 -0.78053

Suplementary Table2. (continue)

isomer atomcoordinate / Å

isomer atomcoordinate / Å

X Y Z X Y Z5E N1 3.22224 -0.03695 0.02444 5G N1 -3.89836 -0.07655 -0.36086

O2 2.93868 -0.04465 -1.06685 O2 -3.73972 0.90563 0.20339O3 1.81591 0.00469 0.99059 O3 -2.55746 -0.91193 -0.38998O4 -0.08138 1.80614 0.08679 O4 -0.25573 -0.45622 0.9452O5 -1.73371 0.03911 -0.65451 O5 1.79167 0.01061 -0.36689O6 -0.12498 -1.75401 0.10399 O6 3.65285 -1.75818 -0.06271O7 -4.19571 -0.06812 0.10634 O7 2.64927 2.43184 -0.08783H8 2.22743 0.00605 1.87192 H8 -2.83649 -1.70104 -0.88218H9 0.65387 1.36468 0.55542 H9 -1.09205 -0.65182 0.46323H10 -0.15696 2.70332 0.4261 H10 -0.25942 -0.9947 1.74303H11 -1.19954 0.84942 -0.35176 H11 0.95071 -0.22387 0.20447H12 -2.67472 0.03987 -0.30698 H12 2.54313 -0.63892 -0.23175H13 -1.20619 -0.77513 -0.33942 H13 2.09618 0.95593 -0.2259H14 -0.26247 -2.62241 0.49557 H14 3.92116 -2.31302 -0.80355H15 0.61478 -1.32276 0.57575 H15 4.42478 -1.69249 0.50992H16 -4.60694 0.22064 0.92781 H16 2.49844 3.00597 0.67092H17 -4.89534 -0.07024 -0.55632 H17 2.715 3.01582 -0.85155

5F N1 3.43747 0.00032 0.49273 5H N1 -2.68555 0.53857 0.51809O2 2.86545 0.0006 1.46824 O2 -1.59936 0.93036 0.27485O3 -1.50291 1.81972 -0.16017 O3 -2.74521 -0.87008 0.32682O4 -0.1182 0.00012 -1.28125 O4 -0.23585 -1.8697 -0.72418O5 -1.50212 -1.81937 -0.15955 O5 1.57476 -0.10808 -0.73022O6 -3.46877 -0.00053 0.83633 O6 0.87276 2.3287 -0.36485O7 2.38876 -0.00087 -0.79383 O7 3.46196 -0.65784 0.92342H8 -1.73791 2.68499 -0.51152 H8 -3.66539 -1.08991 0.55359H9 -2.31752 1.41756 0.18609 H9 -1.13556 -1.6684 -0.42185H10 -0.5944 0.8099 -0.89718 H10 -0.3186 -2.48117 -1.46393H11 -0.5946 -0.80958 -0.89697 H11 0.81001 -0.78578 -0.73491H12 -1.73798 -2.68391 -0.51215 H12 2.28014 -0.34982 -0.05423H13 -2.3164 -1.41677 0.18707 H13 1.25827 0.84191 -0.59913H14 -4.37669 -0.00112 0.50749 H14 1.25716 3.0626 -0.85675H15 -3.56116 0.00021 1.79779 H15 -0.02983 2.58631 -0.14585H16 3.00716 -0.00089 -1.54252 H16 3.3815 -0.96587 1.83237H17 0.86951 -0.00001 -1.04535 H17 4.32864 -0.94676 0.61736

Suplementary Table2. (continue)

isomer atomcoordinate / Å

isomer atomcoordinate / Å

X Y Z X Y Z5I N1 -3.42663 0.07348 -0.39617 5K N1 -0.89117 0.14855 -1.15868

O2 -2.97232 0.93406 0.21818 O2 -1.59418 0.73543 -0.56542O3 -2.39603 -1.06406 -0.55816 O3 -1.7251 -1.87701 -0.70761O4 -0.05309 -1.50167 0.7746 O4 -1.16592 -0.80914 1.70439O5 1.85075 0.08642 0.65271 O5 0.96295 0.18105 0.27O6 3.8614 -0.8397 -0.67194 O6 3.32397 -1.09897 -0.21695O7 1.17148 2.47133 -0.07376 O7 0.16338 2.86446 0.07101H8 -2.89841 -1.71549 -1.07506 H8 -1.49412 -2.74939 -1.04528H9 -0.90793 -1.34814 0.31762 H9 -1.57166 -1.89126 0.25693H10 -0.26033 -1.88774 1.6323 H10 -1.33679 -0.97926 2.63627H11 1.02685 -0.54778 0.6932 H11 -0.22953 -0.56422 1.62833H12 2.60805 -0.30669 0.1232 H12 1.827 -0.24087 0.07672H13 1.61405 1.00618 0.32915 H13 1.1176 1.13799 0.31821H14 3.82489 -1.5149 -1.35828 H14 3.93727 -1.38508 0.4678H15 4.71536 -0.95012 -0.23891 H15 3.79778 -1.22107 -1.04584H16 1.24694 3.19533 0.55813 H16 -0.07439 3.34392 0.87348H17 1.31941 2.86402 -0.94112 H17 0.5443 3.54283 -0.49913

5J N1 -2.27561 -1.58669 0.0092 5L N1 -2.03248 -1.60072 -0.22724O2 -2.47836 -1.08412 -0.97584 O2 -2.23021 -0.80336 -0.99302O3 -0.94887 -0.80913 0.80912 O3 -0.67295 -1.14246 0.7707O4 1.19966 -0.28122 -0.58272 O4 1.30053 -0.19938 -0.58307O5 1.00511 2.17042 -0.59086 O5 0.26174 2.04271 -0.78288O6 -1.3161 2.05343 0.69506 O6 -1.6301 1.5274 1.04469O7 3.42325 -1.2196 0.34729 O7 3.6878 -0.59062 0.32264H8 -0.89667 -1.36187 1.6078 H8 -0.6037 -1.93241 1.33335H9 0.43186 -0.58392 -0.00921 H9 0.61069 -0.67055 -0.00847H10 2.07402 -0.61221 -0.21677 H10 2.22584 -0.29484 -0.20847H11 1.16723 0.77786 -0.64282 H11 0.99427 0.78922 -0.67776H12 1.00802 2.67624 -1.41085 H12 0.64246 2.91685 -0.9108H13 0.14488 2.33945 -0.13614 H13 -0.43915 2.10233 -0.09696H14 -1.71764 2.63534 1.34875 H14 -2.08796 2.03291 1.72457H15 -1.36261 1.15553 1.05644 H15 -1.37691 0.6857 1.45005H16 4.04456 -0.73177 0.89915 H16 4.35405 -1.00042 -0.24028H17 3.95808 -1.82604 -0.17722 H17 4.17331 -0.09802 0.99292

Suplementary Table2. (continue)

isomer atomcoordinate / Å

isomer atomcoordinate / Å

X Y Z X Y Z5M N1 1.49808 -0.7348 1.22056 5O N1 2.41289 -0.93667 -0.44005

O2 0.83798 0.09182 1.48411 O2 1.54956 -1.07634 -1.146O3 0.52416 -1.72591 -0.62928 O3 -0.5992 -1.43396 0.94795O4 -1.28606 0.04643 -0.00685 O4 0.28892 1.14322 1.14411O5 0.66666 2.03395 -0.25321 O5 -1.52635 1.71886 -0.73521O6 2.56536 0.07194 -0.82917 O6 -3.10283 -0.68047 -0.26121O7 -4.01845 -0.03109 -0.13138 O7 2.45717 0.87923 0.06944H8 0.30491 -2.65526 -0.76263 H8 -0.67942 -2.11631 1.62934H9 -0.3271 -1.22291 -0.59272 H9 -1.49724 -1.34777 0.57097H10 -2.26332 0.05555 -0.05801 H10 -0.06078 0.23824 1.31124H11 -0.97391 0.91303 -0.30975 H11 -0.36486 1.53015 0.50656H12 0.64789 2.99193 -0.35134 H12 -1.91184 2.56259 -1.00677H13 1.41666 1.72671 -0.78412 H13 -2.26707 1.09096 -0.67388H14 3.47962 0.04614 -1.13494 H14 -3.8784 -0.63016 0.3179H15 2.10879 -0.65985 -1.27482 H15 -3.42362 -1.15804 -1.04105H16 -4.5578 -0.1267 -0.92276 H16 3.18722 0.94928 0.71366H17 -4.63948 0.17788 0.57349 H17 1.46769 1.03342 0.59965

5N N1 -1.58123 -1.61066 -0.57601 5P N1 -2.39083 -0.31293 0.97319O2 -1.74216 -0.66489 -1.13037 O2 -1.42215 -0.72349 1.33374O3 -0.33004 -1.28898 0.82515 O3 -2.12108 0.63082 -0.59882O4 1.31958 -0.06931 -0.43611 O4 -0.2008 2.03386 -0.27125O5 -0.34881 1.96755 -0.65661 O5 1.29253 0.07524 0.08604O6 -2.22271 0.92325 1.13349 O6 -0.40733 -1.83284 -1.056O7 3.89419 -0.04754 0.28119 O7 3.99582 -0.09243 0.2775H8 -0.05225 -2.17066 1.12174 H8 -2.97382 1.07957 -0.72137H9 0.52632 -0.76396 0.30075 H9 -1.20216 1.41693 -0.47811H10 2.26151 0.00644 -0.15613 H10 0.03186 2.6547 -0.97214H11 0.92254 0.82756 -0.534 H11 0.53874 1.32029 -0.1764H12 -0.28625 2.89677 -0.89865 H12 2.26986 0.01731 0.12486H13 -1.02971 1.901 0.03468 H13 0.95751 -0.69299 -0.40657H14 -2.97004 1.36856 1.5494 H14 -0.18632 -2.73527 -1.31435H15 -1.7805 0.45197 1.8502 H15 -0.93626 -1.4904 -1.78634H16 4.33012 0.43648 0.9901 H16 4.68121 0.13257 -0.3595H17 4.5865 -0.24012 -0.36001 H17 4.45924 -0.24142 1.10791

Suplementary Table2. (continue)

(a) Key isomers for NO+(H2O)4 clusters

4A 4G 4Lr(N1-O2) 1.085 r(N1-O2) 1.127 r(N1-O2) 1.107r(N1-O3) 2.372 r(N1-O3) 1.693 r(N1-O3) 1.901r(N1-O6) 2.539 r(O3-O4) 2.521 r(N1-O5) 3.347r(O3-O5) 2.847 r(O4-O5) 2.572 r(O3-O4) 2.45(O6-N1-O3) 137.1 (O2-N1-O3) 110.5 r(O4-O6) 2.683(O2-N1-O3) 94.6 (N1-O3-O4) 136.8 (O3-N1-O5) 90.3(O3-N1-O4) 84.7 -O4-O5) 112.5 (O2-N1-O3) 107.7(O4-O5-O3) 68.3 (O5-O4-O6) 114.0 N1-O3-O4) 104.4(O2-N1-O3-O5) -105.3 (O2-N1-O3-O4) 31.3 (O3-O4-O6) 123.9q(NO) 0.914 q(HONO) 0.081 (O3-O4-O5) 94.9q(O3) 0.018 q(O4) 0.807 (O2-N1-O3-O4) 68.4q(O4) 0.018 q(O5) 0.056 q(NO) 0.678q(O5) 0.035 q(O6) 0.056 q(O3) 0.185q(O6) 0.014 q(O4) 0.081

q(O5) 0.018q(O6) 0.038

(b) Key isomers for NO+(H2O)5 clusters

5A 5J 5Mr(N1-O2) 1.09 r(N1-O2) 1.124 r(N1-O2) 1.09r(N1-O3) 2.427 r(N1-O3) 1.733 r(N1-O3) 2.314r(O2-O5) 2.751 r(O3-O4) 2.614 r(O2-O4) 2.595r(O7-O4) 2.753 r(O3-O6) 2.888 r(O4-O7) 2.736r(O3-O4) 2.727 r(O4-O5) 2.459 r(O3-O4) 2.609(O3-N1-O7) 92.5 r(O4-O7) 2.586 (O2-N1-O3) 105.3N1-O2-O5) 119.9 (O2-N1-O3) 110 N1-O3-O4) 79.1(N1-O3-O4) 89.7 N1-O3-O4) 118.3 (O3-O4-O5) 88.7O3-O4-O5) 79.4 (O3-O4-O5) 97.9 O3-O4-O7) 131.5(O2-N1-O3-O4) -76.6 O3-O4-O7) 116.2 (O2-N1-O3-O4) -5.4q(NO) 0.879 (O2-N1-O3-O4) -46.4 (N1-O3-O4-O7) -144q(O3) 0.022 (N1-O3-O4-O7) -124.9 q(NO) 0.887q(O4) 0.021 q(HONO) 0.085 q(O3) 0.027q(O5) 0.015 q(O4) 0.72 q(O4) 0.014q(O6) 0.014 q(O5) 0.099 q(O5) 0.009q(O7) 0.049 q(O6) 0.029 q(O6) 0.034

q(O7) 0.068 q(O7) 0.029

Suplementary Table3. Geometrical parameters and natural atomic charges with hydrogen summed into heavy atoms at the MP2/aug-cc-pVTZ level of theory; bond length(r) is given in Å, angles ( and ) in degrees, and charges (q) in electron units.

Toshio et al.