VLFV 7KLVMRXUQDOLV WKH2ZQHU6RFLHWLHV · 2019. 5. 16. · h 6 1.08121203 5 122.37491736 4 178.63165220 o 1 1.45594338 7 107.50452309 6 119.08205659 o 15 1.42273678 1 102.90484263 7

Supporting InformationFormation of Criegee Intermediates and Peroxy Acids: A Computational Study of Gas-phase 1,3-Cycloaddition of

Ozone with Catechol

Debojit Kumar Deb and Biplab Sarkar*Department of Chemistry, Centre for Advanced Studies, North-Eastern Hill University, Shillong 793022, India

Z-matrix coordinates in A of the optimized conformers, transition-states and pre-reactive complexes from B3LYP/6-311+G(2df,2p) calculation.

Ozone

OO 1 1.25328421O 1 1.25328421 2 118.36574646

Catechol

CC 1 1.39848161C 2 1.38540580 1 120.41155891C 3 1.39278244 2 119.92245679 1 −0.00071462C 4 1.38886906 3 119.78343751 2 0.00094534C 1 1.38693374 2 119.46837421 3 0.00000000O 1 1.36212844 6 119.84395957 5 −179.99947300H 7 0.96439840 1 108.68970112 6 179.99725125O 2 1.37616671 1 115.39343914 7 −0.00178868H 9 0.96087868 2 110.44804937 1 179.96746413H 3 1.08386298 2 119.61057443 1 179.99828229H 4 1.08082764 3 119.69751739 2 −180.00000000H 5 1.08106771 4 120.17599779 3 179.99947930H 6 1.08117767 1 118.51837736 7 0.00000000

PR1

CC 1 1.41381857C 2 1.39486646 1 120.03221858C 3 1.38525886 2 119.66026657 1 −0.85793613C 4 1.39768580 3 120.08703256 2 0.87101207C 5 1.38640171 4 120.87055718 3 −0.34295828O 1 1.34582506 6 120.46861137 5 −179.82248483H 7 0.96815815 1 107.91620098 6 177.54447565O 2 1.36189971 1 115.86834794 7 −2.79312184H 9 0.97105446 2 108.55061290 1 133.97703586H 3 1.08095053 2 119.09064398 1 178.38289714H 4 1.08067352 3 119.82076033 2 179.90343321H 5 1.08123021 4 119.73657905 3 179.38904976H 6 1.08063415 5 121.61537952 4 −179.79326004O 9 2.87185276 2 83.51076331 1 123.70421032O 15 1.28532506 9 99.27905264 2 −56.45356272O 16 1.26360793 15 116.49428100 9 −12.24617408

1

Electronic Supplementary Material (ESI) for Physical Chemistry Chemical Physics.This journal is © the Owner Societies 2019

PR2

CC 1 1.40834381C 2 1.39249735 1 120.52860137C 3 1.38557501 2 119.62579964 1 −0.47954630C 4 1.39427502 3 119.91767327 2 0.17807698C 1 1.38765580 2 119.27970587 3 0.50366452O 1 1.35258187 6 119.95060045 5 178.94465690H 7 0.96497094 1 109.23749804 6 177.93367183O 2 1.36350175 1 115.28404483 7 0.16368644H 9 0.96276936 2 110.90214676 1 175.52119691H 3 1.08240130 2 119.46955894 1 179.82649916H 4 1.08038720 3 119.75636256 2 −179.72098952H 5 1.08103325 4 119.87504597 3 179.97310993H 6 1.08072322 1 118.57925992 7 −1.01761683O 2 2.68881284 1 85.63096165 7 87.68477936O 15 1.26296350 2 91.78307723 1 −145.58734757O 16 1.27775908 15 117.01009811 2 −80.30608784

TS1

CC 1 1.46740180C 2 1.42140187 1 118.68360247C 3 1.36203742 2 119.80788685 1 −7.05902304C 4 1.42536606 3 121.15848799 2 6.89506734C 5 1.36044114 4 121.13020663 3 −0.24929780O 1 1.33779642 6 118.20844818 5 161.65090803H 7 0.96677268 1 109.40726159 6 −178.87074381O 2 1.35566856 1 112.80632189 7 −0.50090613H 9 0.96311951 2 110.85815153 1 170.25322161H 3 1.08188553 2 118.59316234 1 176.11788949H 4 1.08104232 3 119.65950148 2 −175.45891430H 5 1.08085761 4 119.06025756 3 177.64669818H 6 1.07980067 5 122.54483892 4 176.07735452O 1 2.04463206 7 96.72462170 6 −100.60320570O 15 1.31695943 1 103.23603019 7 −146.37444629O 16 1.32183070 15 108.94422071 1 51.69496425

2

TS2

CC 1 1.47028439C 2 1.41741501 1 118.24863930C 3 1.36363420 2 119.71348028 1 −10.43431867C 4 1.42636242 3 121.34116399 2 6.82997039C 5 1.35981165 4 121.21194482 3 1.47521057O 1 1.33362933 6 118.48377501 5 158.68016667H 7 0.96898930 1 108.41147883 6 −168.13372201O 2 1.37324077 1 114.97458234 7 2.00726387H 9 0.96964599 2 107.66821637 1 99.13253102H 3 1.08018729 2 117.99091027 1 172.98126886H 4 1.08113292 3 119.66365678 2 −175.12848149H 5 1.08106711 4 118.98662991 3 178.51486172H 6 1.07977995 5 122.65690301 4 174.60269251O 1 2.06329257 7 96.61123773 6 −100.79997623O 15 1.31416034 1 103.16292755 7 −146.33748708O 16 1.32248837 15 109.20330415 1 50.91375360

TS3

CC 1 1.46620174C 2 1.42621553 1 118.12825657C 3 1.35873849 2 119.77012406 1 −8.26030388C 4 1.42849070 3 121.36343485 2 6.73261759C 5 1.35856322 4 121.15799658 3 0.37585777O 1 1.33635501 6 119.12890327 5 161.33453944H 7 0.96822744 1 108.90965663 6 −170.13789165O 2 1.37160413 1 111.82581197 7 −4.41241238H 9 0.96319443 2 110.04132690 1 152.21732772H 3 1.08156420 2 118.55588597 1 174.39458288H 4 1.08121570 3 119.66315497 2 −175.80806799H 5 1.08091729 4 118.98091765 3 177.80852119H 6 1.08000605 5 122.59999705 4 175.44232516O 1 2.13317381 7 99.81276846 6 −99.60826604O 15 1.31657460 1 94.65870787 7 −82.15624474O 16 1.33251670 15 108.11850100 1 −63.58200918

3

POZ1

CC 1 1.59512021C 2 1.49573881 1 115.20053607C 3 1.33350299 2 122.35637206 1 −5.23443842C 4 1.46072124 3 122.37332087 2 2.45509943C 5 1.33145671 4 121.86189900 3 0.99459768O 1 1.37425925 6 108.48219738 5 126.14692946H 7 0.96763827 1 108.50892507 6 −156.92696376O 2 1.39973798 1 109.53493997 7 7.38672147H 9 0.96164482 2 109.86364745 1 −123.31390660H 3 1.08342764 2 115.71030323 1 179.08806446H 4 1.08222078 3 119.59175142 2 −177.19852764H 5 1.08170353 4 118.04976579 3 −179.68371377H 6 1.08121203 5 122.37491736 4 178.63165220O 1 1.45594338 7 107.50452309 6 −119.08205659O 15 1.42273678 1 102.90484263 7 −151.06756234O 16 1.43462052 15 102.38468363 1 50.58269535

POZ2

CC 1 1.58270808C 2 1.49737262 1 114.63374425C 3 1.33289857 2 121.13259094 1 −17.67921572C 4 1.46294048 3 122.30915355 2 3.90818522C 5 1.33168928 4 121.94178237 3 5.96479262O 1 1.37146859 6 109.41804293 5 114.04868419H 7 0.96987438 1 107.78502860 6 −151.00225003O 2 1.40979442 1 109.91728074 7 19.93671073H 9 0.96616343 2 107.00935953 1 90.59266833H 3 1.08063063 2 116.12346235 1 165.54506176H 4 1.08195798 3 119.68864640 2 −176.49281835H 5 1.08183725 4 118.03934984 3 −175.96189628H 6 1.08105170 5 122.63690990 4 176.98440358O 1 1.45935064 7 107.39357506 6 −121.31460210O 15 1.40803153 1 102.21291913 7 −160.95979276O 2 1.43021969 1 104.40743444 7 134.07709434

4

POZ3

CC 1 1.59478615C 2 1.49651951 1 115.64302953C 3 1.33378150 2 121.86611731 1 −2.70981401C 4 1.45752042 3 122.52561503 2 1.34811335C 5 1.33293459 4 122.31837707 3 0.63521740O 1 1.37967594 6 109.11290027 5 127.43002124H 7 0.96668912 1 108.91161968 6 −150.03901947O 2 1.41132330 1 106.85458346 7 2.02977737H 9 0.96295448 2 108.77010210 1 157.48988865H 3 1.08219351 2 116.38415897 1 176.91410205H 4 1.08203337 3 119.49163904 2 179.95972011H 5 1.08171825 4 117.95512177 3 178.82447230H 6 1.08090366 5 122.37168579 4 176.96353006O 1 1.44210131 7 112.38514069 6 −116.76071376O 15 1.42651478 1 103.65628229 7 −89.05926029O 2 1.41603783 1 103.81165488 7 119.39710127

TS4a


5

TS4b

CC 1 1.59628015C 2 1.49528753 1 115.49698650C 3 1.33212303 2 122.23743184 1 −5.54745430C 4 1.46180221 3 122.30881338 2 3.02812508C 5 1.33255582 4 122.00389878 3 0.53050822O 1 1.39713771 6 111.41806078 5 127.24281050H 7 0.96470622 1 108.59673992 6 −85.22476279O 2 1.38743930 1 112.64571016 7 1.22772867H 9 0.96687157 2 108.27064134 1 59.65485681H 3 1.08099092 2 115.28617847 1 175.98937178H 4 1.08199928 3 119.67962311 2 −177.84210522H 5 1.08206789 4 118.02709824 3 179.63113338H 6 1.08142100 5 122.45154757 4 178.75205576O 1 1.43732174 7 103.66759050 6 −119.11772468O 15 1.42766331 1 102.54765126 7 −149.61266390O 16 1.42868622 15 102.48512660 1 50.74354895

TS4c


6

TS5

CC 1 1.80019696C 2 1.49722276 1 108.51049063C 3 1.33168866 2 121.57201873 1 34.73146760C 4 1.46247468 3 121.99318306 2 −5.09921339C 5 1.32950037 4 121.91204906 3 −15.22158897O 1 1.39675592 6 108.83234033 5 146.27650573H 7 0.96430734 1 107.62050066 6 157.31903167O 2 1.35911590 1 111.25075970 7 −32.30972804H 9 0.96316211 2 109.47194774 1 −113.67357101H 3 1.08269349 2 115.65560856 1 −148.65396443H 4 1.08210475 3 119.64423991 2 174.86729376H 5 1.08180208 4 118.22832755 3 165.41135592H 6 1.08119458 5 122.49241948 4 179.05096022O 1 1.29109096 7 117.05583085 6 −132.50968255O 15 1.90682886 1 102.79216497 7 −100.05692599O 16 1.32674702 15 97.11903541 1 13.75287107

TS6

CC 1 1.80128622C 2 1.52005746 1 104.72933981C 3 1.32875837 2 123.28945765 1 −31.80967507C 4 1.46265286 3 122.44084281 2 4.12064467C 5 1.32937537 4 122.00898220 3 15.51038050O 1 1.34780764 6 114.12605709 5 90.19928816H 7 0.97340581 1 107.40056142 6 −159.29929699O 2 1.42308094 1 102.48229258 7 32.46444142H 9 0.96544250 2 106.34246870 1 103.49176641H 3 1.08124685 2 114.09721719 1 151.19800653H 4 1.08198859 3 119.50816988 2 −175.26416439H 5 1.08175285 4 118.25428886 3 −164.85181603H 6 1.08195682 5 122.67161398 4 −179.09408252O 1 1.38790755 7 110.52016384 6 −132.83069704O 15 1.32030096 1 109.56805267 7 −171.86341135O 2 1.27962079 1 105.61805637 7 154.67148489

7

TS7

CC 1 1.82064149C 2 1.47587887 1 113.51312062C 3 1.33546217 2 121.45673890 1 −21.00289451C 4 1.45637801 3 123.92678524 2 4.96511290C 5 1.33272583 4 123.46765199 3 10.07610861O 1 1.40105973 6 109.59704613 5 102.21461804H 7 0.96434505 1 107.45528359 6 137.69389873O 2 1.35443976 1 107.18487964 7 32.00015552H 9 0.96906096 2 107.94531803 1 65.95217922H 3 1.08152950 2 116.34599885 1 157.90359340H 4 1.08251380 3 118.77585721 2 −178.12766076H 5 1.08220213 4 117.33993117 3 −173.75267679H 6 1.08174159 5 121.24890812 4 175.79711596O 1 1.30601250 7 115.61426653 6 −129.88593261O 15 1.84757579 1 104.39001762 7 −111.57198923O 16 1.33566818 15 94.76675390 1 −34.94775603

TS8

CC 1 1.92651455C 2 1.50484120 1 106.98747146C 3 1.33348414 2 125.94912446 1 1.63583048C 4 1.45536716 3 125.07848692 2 6.06382244C 5 1.33536506 4 124.50066560 3 −6.35509712O 1 1.35096234 6 115.19579267 5 130.57406690H 7 0.97586455 1 108.43365944 6 −113.33969699O 2 1.42347786 1 101.49742033 7 −18.35130854H 9 0.96681423 2 105.63104392 1 117.36910181H 3 1.08249934 2 113.49664409 1 −176.46945729H 4 1.08252253 3 118.10374297 2 −177.80875669H 5 1.08258372 4 116.75074340 3 169.49298295H 6 1.08295382 5 121.44838347 4 172.03514092O 1 1.37141348 7 115.74716148 6 −131.44097905O 15 1.31652741 1 111.28353617 7 −54.98431027O 2 1.27387338 1 104.26485880 7 101.81760350

8

CI1#

CC 1 3.53301474C 2 1.43996593 1 79.50730786C 3 1.34306578 2 127.92485216 1 40.09145548C 4 1.46031347 3 131.07510442 2 −5.76715367C 5 1.34530123 4 131.42742906 3 −53.05199008O 1 1.35395302 6 110.13556679 5 −169.51927073H 7 0.96836840 1 107.29086890 6 179.53418918O 2 1.32734500 1 68.37474001 7 −41.15770624H 9 0.96630017 2 110.32576559 1 −49.65926463H 3 1.08156805 2 111.49073950 1 −143.60758818H 4 1.08589801 3 115.79664173 2 169.51205378H 5 1.08704963 4 113.15205882 3 132.52726361H 6 1.08112420 5 118.32053243 4 −176.59057872O 1 1.20444329 7 122.88507741 6 −179.34894382O 2 2.28384162 1 128.14386007 15 10.35167396O 2 1.26829057 1 131.62322320 15 −31.90427717

CI2#

CC 1 3.48608654C 2 1.47518108 1 82.53271786C 3 1.34044917 2 126.89337147 1 −33.89361825C 4 1.45794977 3 131.68039132 2 −0.15670940C 5 1.34253279 4 132.19707635 3 50.89356826O 1 1.32692133 6 121.48037388 5 17.45841361H 7 0.96851147 1 108.88985750 6 179.76409262O 2 1.35746883 1 153.02829497 7 47.41065905H 9 0.96794430 2 107.02774634 1 66.28203135H 3 1.08086789 2 114.72655336 1 150.61703365H 4 1.08668349 3 115.24295382 2 −173.16911858H 5 1.08647667 4 112.63162503 3 −132.05249202H 6 1.08149752 5 120.47734476 4 −176.32445984O 1 1.26868557 7 115.78534575 6 −174.39733680O 15 1.39807088 1 118.89083285 7 −178.80304312O 2 1.20631761 1 50.86514821 15 26.99028395

9

POA1#

CC 1 3.67525013C 2 1.47236246 1 79.98583592C 3 1.33538615 2 129.04259975 1 −33.52357177C 4 1.46447813 3 131.61136124 2 −2.23463116C 5 1.33713455 4 132.13532685 3 59.04181685O 1 1.35200589 6 115.38462736 5 0.41248619H 7 0.96808143 1 106.77723665 6 179.56014428O 2 1.21144716 1 123.20212270 7 41.93713392H 9 1.86563823 2 84.53139662 1 79.59540791H 3 1.08134372 2 111.89238586 1 144.42382023H 4 1.08700721 3 115.47706828 2 −177.94434750H 5 1.08729034 4 112.36964204 3 −126.22445764H 6 1.08078181 5 118.25463761 4 177.38873520O 1 1.20702945 7 122.23809087 6 −179.08860338O 2 2.29653592 1 83.30352276 15 29.59548844O 2 1.34918403 1 66.52319006 15 62.27765899

CI4#

CC 1 3.61099614C 2 1.47602742 1 78.30260371C 3 1.33938880 2 130.88429843 1 33.98571846C 4 1.46005861 3 132.76881122 2 0.26930158C 5 1.34265862 4 131.45984307 3 −54.41356403O 1 1.32137357 6 121.40356711 5 157.41616850H 7 0.96401241 1 110.21850396 6 −5.30357900O 2 1.35447595 1 48.92257314 7 −36.63107564H 9 0.96834237 2 106.19474112 1 133.96304331H 3 1.08066883 2 111.18680555 1 −148.53678989H 4 1.08716767 3 114.87503592 2 174.40153595H 5 1.08604453 4 113.08195658 3 130.16604042H 6 1.08430118 5 117.69063597 4 179.61710352O 1 1.26224374 7 118.67906852 6 −178.13871567O 15 1.38413890 1 118.19141171 7 −3.98432912O 2 1.20617294 1 144.75103158 15 −58.56143496

10

TS9

CC 1 3.96237414C 2 1.44240914 1 70.17338265C 3 1.33903030 2 127.10535917 1 39.12638967C 4 1.47321043 3 129.33539770 2 2.63687075C 5 1.33848881 4 129.10268292 3 −80.30219938O 1 1.35177677 6 110.41591991 5 178.45223104H 7 0.96850698 1 107.51748046 6 179.58582369O 2 1.32954993 1 65.02829800 7 −27.90941020H 9 0.96737876 2 110.37435798 1 −33.88786613H 3 1.08009502 2 111.96051494 1 −142.18952486H 4 1.08655331 3 116.69721686 2 176.76278743H 5 1.08809884 4 114.27524861 3 103.66650559H 6 1.08120515 5 119.46984557 4 −178.21590599O 1 1.20352025 7 123.29648645 6 −179.24429488O 2 2.29331561 1 140.40806788 15 3.82325042O 2 1.26624539 1 145.94468921 15 −50.39461023

TS10

CC 1 3.92678486C 2 1.47741360 1 72.94341165C 3 1.33269883 2 124.14879756 1 −38.30693274C 4 1.47016038 3 129.05530116 2 −1.48600812C 5 1.33993002 4 130.35457976 3 80.81552865O 1 1.33013884 6 121.42582767 5 −1.26711667H 7 0.96902436 1 108.78723155 6 179.15142119O 2 1.35541155 1 138.42360123 7 31.77095979H 9 0.96803252 2 107.15100209 1 93.11587052H 3 1.08054944 2 116.15646386 1 142.24715974H 4 1.08762955 3 116.96878729 2 −176.77915724H 5 1.08722715 4 113.58479936 3 −104.81027959H 6 1.07991952 5 121.01228841 4 176.04688484O 1 1.26837160 7 115.44211021 6 −179.40396413O 15 1.40156098 1 119.52644961 7 178.66489491O 2 1.20544191 1 68.18325043 15 51.62140601

11

TS11

CC 1 4.04440158C 2 1.47138110 1 70.94971055C 3 1.33346797 2 128.78984783 1 −37.05850683C 4 1.47066389 3 130.09795872 2 −3.32612358C 5 1.33378726 4 130.33393621 3 79.54132626O 1 1.35292839 6 114.95596672 5 2.10404313H 7 0.96805349 1 106.67976367 6 179.61989182O 2 1.21209410 1 134.15334572 7 51.07399839H 9 1.86035609 2 84.69746065 1 84.46490700H 3 1.08097036 2 111.83864306 1 141.27396134H 4 1.08738537 3 116.08907966 2 −178.90711477H 5 1.08773420 4 113.26272303 3 −104.94671923H 6 1.08051999 5 118.92438864 4 177.57486121O 1 1.20680643 7 122.30617242 6 −179.31663754O 2 2.29755094 1 88.89894662 15 30.45175146O 2 1.35101399 1 65.28744636 15 58.00382719

TS12

CC 1 4.03954840C 2 1.47603505 1 68.28231940C 3 1.33401009 2 128.94014395 1 39.09574890C 4 1.46988785 3 130.06804720 2 1.52901932C 5 1.33893919 4 128.67553050 3 −81.16848365O 1 1.32155310 6 121.50888779 5 164.66216539H 7 0.96387282 1 110.38462394 6 −4.08957585O 2 1.35556935 1 57.96528798 7 −46.84559310H 9 0.96818964 2 106.28154699 1 141.01321259H 3 1.08034720 2 112.18557162 1 −141.99547543H 4 1.08786623 3 116.28624223 2 177.23258974H 5 1.08617274 4 114.67789424 3 103.23563314H 6 1.08367020 5 118.13696769 4 −178.86357496O 1 1.26317933 7 118.56284295 6 −178.56085292O 15 1.38541892 1 118.28697055 7 −2.08227301O 2 1.20604964 1 147.47433694 15 −58.89268755

12

CI1a

CC 1 5.40085572C 2 1.43779042 1 41.10932560C 3 1.35202514 2 127.46041353 1 4.80295959C 4 1.44626686 3 126.04325472 2 10.73189451C 5 1.34676555 4 126.68959535 3 −174.10107979O 1 1.35386620 6 110.47547788 5 −177.39027096H 7 0.96811575 1 107.30783729 6 179.83166347O 2 1.33464658 1 86.18250210 7 33.80020492H 9 0.96422464 2 110.09688327 1 30.01499411H 3 1.08235011 2 111.96740375 1 −175.50512917H 4 1.08032075 3 117.65458318 2 −172.52218382H 5 1.08431228 4 117.20905599 3 8.95237627H 6 1.08061973 5 119.14464629 4 −177.18084989O 1 1.20832048 7 122.36464371 6 179.91475600O 2 2.25695515 1 125.12206214 15 52.99832136O 2 1.26573522 1 157.74310618 15 67.78419636

CI1b

CC 1 5.50016226C 2 1.43767763 1 42.53956457C 3 1.35212364 2 127.70387196 1 4.10870589C 4 1.44602238 3 126.04339834 2 10.38850619C 5 1.34757956 4 128.36802509 3 −174.19255305O 1 1.35491931 6 115.52410552 5 0.74766535H 7 0.96835362 1 106.78792150 6 −179.72077874O 2 1.33424614 1 85.10421066 7 −142.74649414H 9 0.96417609 2 110.21789650 1 30.45926762H 3 1.08239531 2 111.79256159 1 −176.33745997H 4 1.07917281 3 117.02041865 2 −173.06938245H 5 1.08459761 4 116.42724372 3 8.62575878H 6 1.08083927 5 118.44349385 4 −177.78810570O 1 1.20680958 7 122.08976809 6 −179.79296141O 2 2.25751890 1 126.05237951 15 −140.04713502O 2 1.26594425 1 158.33595754 15 −122.98185129

13

CI1c

CC 1 5.55168119C 2 1.42713415 1 39.79367485C 3 1.35497179 2 128.94780139 1 0.00030370C 4 1.44258775 3 127.54073174 2 0.00114492C 5 1.34869932 4 127.49211180 3 −180.00000000O 1 1.35499400 6 115.86228239 5 0.00043642H 7 0.96826300 1 106.71227705 6 180.00000000O 2 1.33386181 1 82.53759988 7 −179.99475164H 9 0.96912644 2 108.89917469 1 −179.99789945H 3 1.08077205 2 110.97455725 1 180.00000000H 4 1.07935331 3 115.94442915 2 −179.99937397H 5 1.08017239 4 116.65365699 3 0.00030362H 6 1.08098932 5 118.18482752 4 −180.00000000O 1 1.20746260 7 121.88548405 6 −179.99973285O 2 2.30846909 1 131.28459127 15 −179.99378084O 2 1.27377429 1 162.79328169 15 −179.99145668

CI1d

CC 1 5.45454609C 2 1.42718552 1 38.24630806C 3 1.35468850 2 128.76947985 1 0.00234739C 4 1.44329639 3 127.57858078 2 0.00408834C 5 1.34775389 4 125.80146784 3 −179.99744737O 1 1.35522220 6 110.30795570 5 −179.99900660H 7 0.96802850 1 107.17723822 6 180.00000000O 2 1.33441219 1 84.02890334 7 0.01180668H 9 0.96907949 2 108.82833676 1 −179.99725798H 3 1.08075641 2 111.11261791 1 −179.99737801H 4 1.08065168 3 116.60541029 2 −179.99713806H 5 1.08001246 4 117.46700690 3 0.00280373H 6 1.08077109 5 118.85306694 4 −179.99918808O 1 1.20836539 7 122.11654254 6 −180.00000000O 2 2.30849904 1 129.88737680 15 0.01754841O 2 1.27377564 1 161.37572350 15 0.01960256

14

TS13a

CC 1 5.37387105C 2 1.43705396 1 38.99371822C 3 1.34981168 2 127.14963868 1 4.86829286C 4 1.44842142 3 127.56292531 2 9.51938616C 5 1.33848585 4 124.26114478 3 −173.75313216O 1 1.34854064 6 112.18033592 5 90.54187250H 7 0.97004878 1 107.67177019 6 177.26362799O 2 1.33531380 1 87.75248237 7 −72.49648907H 9 0.96402130 2 110.09423714 1 28.46688955H 3 1.08193579 2 112.05363553 1 −175.97299264H 4 1.08386418 3 116.29795927 2 −174.12320825H 5 1.08325036 4 118.24643050 3 9.13775790H 6 1.08273399 5 120.36087075 4 −177.94865400O 1 1.20141772 7 123.51385944 6 −178.34679261O 2 2.26206073 1 124.15525069 15 −19.77025999O 2 1.26513994 1 156.99189932 15 −8.01649529

TS13b

CC 1 5.53694813C 2 1.42449135 1 40.63909930C 3 1.35807059 2 128.47610569 1 1.96683361C 4 1.44188890 3 127.17619102 2 5.87108470C 5 1.34910762 4 127.71712976 3 −177.69265038O 1 1.35530301 6 115.79197013 5 0.39886438H 7 0.96826684 1 106.69346015 6 −179.78190397O 2 1.35046611 1 84.23216587 7 −164.86099789H 9 0.96511892 2 111.79089094 1 89.04806785H 3 1.08125485 2 112.03476942 1 −178.17845293H 4 1.07934469 3 116.18196703 2 −176.26813106H 5 1.08102417 4 116.37731452 3 3.61765374H 6 1.08098322 5 118.23881304 4 −178.63526138O 1 1.20748406 7 121.88632761 6 −179.88792041O 2 2.28392748 1 130.79116430 15 −162.31635161O 2 1.27718408 1 161.98715053 15 −154.98542617

15

TS13c

CC 1 5.40516294C 2 1.42675566 1 36.49894297C 3 1.35256915 2 128.15927637 1 −0.42241914C 4 1.44359756 3 128.96981772 2 −0.06130406C 5 1.33962378 4 123.31045102 3 −179.34361030O 1 1.34847512 6 112.29381258 5 91.04997939H 7 0.96995791 1 107.62976232 6 177.18000621O 2 1.33443142 1 85.50801016 7 −108.19435579H 9 0.96898314 2 108.77534022 1 −179.99393415H 3 1.08041023 2 111.30814702 1 179.64284278H 4 1.08433942 3 115.24941246 2 179.79836233H 5 1.07906816 4 118.38925081 3 0.84962493H 6 1.08296810 5 120.22294026 4 −179.64752744O 1 1.20201870 7 123.40876966 6 −178.13713179O 2 2.30785562 1 127.93872187 15 −67.53394411O 2 1.27214035 1 159.68027457 15 −67.50014833

TS13d


16

CI2a

CC 1 5.45456609C 2 1.47663781 1 42.37441663C 3 1.34775302 2 126.41977182 1 0.00151289C 4 1.44330169 3 125.80094183 2 0.00000000C 5 1.35468782 4 127.58044365 3 −179.99513824O 1 1.33441242 6 122.27561919 5 −0.01554049H 7 0.96907930 1 108.82815403 6 −179.99809209O 2 1.35522309 1 152.68260071 7 −0.01379494H 9 0.96802813 2 107.17725232 1 179.99873226H 3 1.08077197 2 114.72712984 1 −179.99900393H 4 1.08000964 3 116.73176801 2 −180.00000000H 5 1.08065168 4 115.81544977 3 0.00256672H 6 1.08075412 5 120.11722453 4 179.99358618O 1 1.27377725 7 114.59441303 6 179.99641956O 15 1.39163051 1 119.95387696 7 179.99517528O 2 1.20836527 1 85.20081380 15 −0.03842602

CI2b

CC 1 5.40031392C 2 1.47615687 1 42.25147687C 3 1.34676508 2 125.67296831 1 −7.36029412C 4 1.44628541 3 126.71126478 2 −2.39021473C 5 1.35202422 4 126.02286764 3 174.05774827O 1 1.33461202 6 124.72743840 5 −28.24613822H 7 0.96420970 1 110.09131198 6 −14.82586394O 2 1.35387571 1 152.47895406 7 −34.10416715H 9 0.96810186 2 107.30229654 1 173.37768465H 3 1.08061340 2 115.18279902 1 173.09580644H 4 1.08431582 3 116.04012718 2 −179.34937852H 5 1.08030606 4 116.25248913 3 −9.16789805H 6 1.08233602 5 120.57819597 4 168.89165294O 1 1.26574180 7 113.26442462 6 176.00080679O 15 1.39368634 1 116.04662346 7 171.34614567O 2 1.20830595 1 84.99833382 15 −68.05647716

17

CI2c

CC 1 5.49985659C 2 1.47578314 1 37.74590076C 3 1.34757571 2 130.25549894 1 −7.80288190C 4 1.44602229 3 128.39216902 2 −2.33547003C 5 1.35213227 4 126.02337266 3 174.16067762O 1 1.33421672 6 124.89068509 5 −28.07555608H 7 0.96415304 1 110.21249521 6 −14.47241814O 2 1.35489871 1 78.01989207 7 142.63432518H 9 0.96834537 2 106.78629561 1 −175.87756231H 3 1.08082279 2 111.30331608 1 172.10378661H 4 1.08459216 3 115.14894384 2 −179.53484754H 5 1.07916618 4 116.87122345 3 −9.30642436H 6 1.08238185 5 120.50779439 4 169.09131889O 1 1.26595687 7 113.25540288 6 175.91204952O 15 1.39348837 1 116.09129943 7 171.48211214O 2 1.20681870 1 159.44627656 15 122.87259323

CI2d

CC 1 5.55158778C 2 1.47592097 1 37.90953766C 3 1.34869319 2 130.88014914 1 0.02126103C 4 1.44257892 3 127.49155695 2 0.01713132C 5 1.35497300 4 127.54161361 3 −179.96786984O 1 1.33386167 6 122.33156103 5 −0.04184920H 7 0.96912632 1 108.89923708 6 −179.99873097O 2 1.35499372 1 77.94996623 7 179.98994017H 9 0.96826341 2 106.71227223 1 179.98306247H 3 1.08098874 2 110.93363607 1 −179.96854638H 4 1.08017304 3 115.85486277 2 −179.98485624H 5 1.07935591 4 116.51502074 3 0.02714983H 6 1.08076935 5 120.07943912 4 179.98523833O 1 1.27378073 7 114.66937607 6 179.99185135O 15 1.39199908 1 119.91928176 7 179.99132343O 2 1.20746383 1 160.16351141 15 179.83235982

18

TS14a

CC 1 5.43820231C 2 1.47598709 1 42.37892691C 3 1.34823295 2 126.23331409 1 −3.56589110C 4 1.44240351 3 126.02328903 2 −1.58287739C 5 1.35781940 4 127.21430668 3 177.42041669O 1 1.35104148 6 124.54839737 5 −8.73877185H 7 0.96508443 1 111.72418869 6 −85.05106985O 2 1.35513326 1 152.72423356 7 −14.59258214H 9 0.96801313 2 107.18736096 1 177.39159222H 3 1.08075767 2 114.84032381 1 176.63065206H 4 1.08079717 3 116.77356310 2 179.90398912H 5 1.08056609 4 115.92765421 3 −4.60234548H 6 1.08125505 5 119.54248489 4 173.78151609O 1 1.27708232 7 113.09104856 6 −179.38136878O 15 1.36666497 1 119.45080688 7 174.26744327O 2 1.20857737 1 85.11074289 15 −29.72194264

TS14b

CC 1 5.37286486C 2 1.49421725 1 44.46770748C 3 1.33847689 2 124.83239275 1 −7.15599207C 4 1.44846515 3 124.27119876 2 0.63071368C 5 1.34982170 4 127.55590888 3 173.47375321O 1 1.33533626 6 124.61949733 5 −26.52056378H 7 0.96403308 1 110.11460302 6 −14.94898824O 2 1.34854067 1 101.21718929 7 72.51689522H 9 0.97003787 2 107.67819589 1 137.53583522H 3 1.08272958 2 114.75550079 1 175.40257607H 4 1.08318802 3 117.44092833 2 −176.50560357H 5 1.08386893 4 116.05650251 3 −10.13309820H 6 1.08191739 5 120.79569586 4 169.63576974O 1 1.26519801 7 113.21933766 6 176.20201216O 15 1.39525644 1 116.40884713 7 172.13700507O 2 1.20141690 1 119.03935083 15 8.35186995

19

TS14c

CC 1 5.53712732C 2 1.47540691 1 37.86326031C 3 1.34910681 2 130.74655395 1 −3.57836856C 4 1.44189150 3 127.71623406 2 −1.47728049C 5 1.35806746 4 127.18164372 3 177.69845541O 1 1.35046889 6 124.66466781 5 −8.60464937H 7 0.96511901 1 111.79003117 6 −84.71517520O 2 1.35530122 1 77.97817440 7 164.89062119H 9 0.96826634 2 106.69360394 1 −178.23120276H 3 1.08098406 2 111.01474791 1 176.31257144H 4 1.08101815 3 115.89264254 2 179.82848081H 5 1.07934639 4 116.60757555 3 −4.44508032H 6 1.08125194 5 119.48641056 4 173.98376026O 1 1.27718535 7 113.11257567 6 −179.31566708O 15 1.36687226 1 119.46001087 7 174.28332468O 2 1.20748295 1 160.04144175 15 155.01565096

TS14d

CC 1 5.40529537C 2 1.49383954 1 45.06969321C 3 1.33962940 2 125.22240969 1 −0.59813133C 4 1.44360190 3 123.31475387 2 2.44348771C 5 1.35256874 4 128.96918696 3 179.34810721O 1 1.33443205 6 122.00683006 5 0.59841125H 7 0.96898360 1 108.77525593 6 179.87390973O 2 1.34847327 1 105.86335635 7 108.14069296H 9 0.96995922 2 107.62992378 1 135.43344403H 3 1.08296931 2 114.50358703 1 −177.94361630H 4 1.07906723 3 118.29804498 2 −177.36248676H 5 1.08433699 4 115.78234497 3 −0.79691453H 6 1.08041018 5 120.53240253 4 −179.87930961O 1 1.27214024 7 114.81176371 6 −179.93562686O 15 1.39676715 1 119.62835969 7 −179.80639141O 2 1.20201810 1 114.33448981 15 67.42262758

20

POA1a

CC 1 5.61516232C 2 1.47037013 1 37.66601852C 3 1.34642160 2 131.20098600 1 0.00049847C 4 1.44783543 3 127.68410976 2 0.00000000C 5 1.34619395 4 127.47157420 3 −180.00000000O 1 1.35593833 6 115.94187697 5 −0.01235299H 7 0.96822605 1 106.55297499 6 180.00000000O 2 1.21254745 1 161.40582566 7 −0.02972801H 9 1.85424437 2 85.07846583 1 −179.98478201H 3 1.08135365 2 110.40541159 1 −179.99838597H 4 1.07964340 3 115.95886993 2 −180.00000000H 5 1.08038991 4 116.58791152 3 −0.00089898H 6 1.08102113 5 118.14064224 4 179.99800648O 1 1.20721894 7 121.73546369 6 179.99942418O 2 2.30158487 1 113.00891002 15 −0.03168956O 2 1.35457354 1 77.53276298 15 −0.03562407

POA1b

CC 1 5.51594768C 2 1.47050064 1 36.10316408C 3 1.34598170 2 131.01718606 1 −0.01113502C 4 1.44818049 3 127.73391457 2 −0.00406161C 5 1.34530382 4 125.73201617 3 179.98885576O 1 1.35501653 6 110.31294627 5 179.98616819H 7 0.96797211 1 107.16342545 6 −179.99934975O 2 1.21249007 1 159.94607206 7 179.92575954H 9 1.85274141 2 85.12039899 1 −179.98081021H 3 1.08139042 2 110.51264367 1 179.99602315H 4 1.08081457 3 116.65965851 2 −179.99937034H 5 1.08014677 4 117.39221159 3 −0.01518859H 6 1.08075210 5 118.84854036 4 179.99246256O 1 1.20865918 7 122.02411477 6 −179.99968401O 2 2.30199026 1 114.52215741 15 179.95274724O 2 1.35530586 1 79.04438408 15 179.94830094

21

TS15

CC 1 5.46438406C 2 1.46780201 1 34.48494610C 3 1.34485185 2 130.31769986 1 0.32451891C 4 1.44802902 3 129.12571171 2 −0.21452687C 5 1.33748368 4 123.27081926 3 179.36126160O 1 1.34943079 6 112.31971986 5 −90.25201828H 7 0.96985352 1 107.52065317 6 −176.98316906O 2 1.21283388 1 158.55079923 7 −74.07507664H 9 1.85133332 2 85.10826577 1 −178.55900025H 3 1.08093529 2 110.91418467 1 −179.58814887H 4 1.08459841 3 115.27516040 2 −179.87584452H 5 1.07915338 4 118.30806378 3 −0.95738224H 6 1.08301977 5 120.18180227 4 179.46593209O 1 1.20229691 7 123.22658323 6 178.15320137O 2 2.30183952 1 115.92668700 15 −113.76436641O 2 1.35592511 1 80.43705717 15 −114.14000199

CI4a


22

CI4b

CC 1 5.47151649C 2 1.47546731 1 42.53800782C 3 1.34822812 2 126.27460510 1 0.51404366C 4 1.44134331 3 125.61905888 2 0.15631504C 5 1.35518532 4 127.18961551 3 −179.36069671O 1 1.32216200 6 121.42384579 5 −178.40515977H 7 0.96375988 1 110.45147721 6 0.41848409O 2 1.35456447 1 152.98328924 7 −176.91086999H 9 0.96793698 2 107.20292612 1 −179.34139219H 3 1.08059293 2 114.89255517 1 −179.46900136H 4 1.08045756 3 116.95512834 2 −179.84307586H 5 1.08022830 4 116.10956468 3 0.72310067H 6 1.08406995 5 116.63790266 4 −179.64551721O 1 1.26930563 7 117.80228409 6 179.87383362O 15 1.38234420 1 118.30612461 7 0.32174027O 2 1.20973541 1 85.00968461 15 −177.82573148

POA2a

CC 1 5.61512059C 2 1.47628675 1 38.13528599C 3 1.34619364 2 130.94282747 1 0.00073459C 4 1.44783582 3 127.47235725 2 0.00027153C 5 1.34642061 4 127.68279341 3 −179.99914061O 1 1.21254621 6 123.74072122 5 −179.99722405H 7 1.85424878 1 85.07814024 6 180.00000000O 2 1.35594012 1 77.80657311 7 0.01222810H 9 0.96822539 2 106.55306346 1 −179.99693065H 3 1.08102101 2 110.91643294 1 180.00000000H 4 1.08039169 3 115.94049356 2 179.99964486H 5 1.07964337 4 116.35772142 3 0.00114887H 6 1.08135424 5 118.39433585 4 −179.99926591O 1 1.35457406 7 121.06176283 6 180.00000000O 15 1.43330807 1 111.26078670 7 0.00045543O 2 1.20721961 1 160.45830768 7 −179.98056974

23

POA2b

CC 1 5.51605679C 2 1.47721087 1 42.68498035C 3 1.34530557 2 126.43984371 1 0.00695735C 4 1.44818012 3 125.73157629 2 0.00554093C 5 1.34598517 4 127.73642284 3 −179.99063790O 1 1.21249339 6 123.84075403 5 −179.97462574H 7 1.85271790 1 85.12119597 6 −179.99690673O 2 1.35501634 1 152.99756769 7 −179.92578997H 9 0.96797149 2 107.16350326 1 179.99218330H 3 1.08075116 2 114.71215118 1 −179.99369368H 4 1.08014349 3 116.87562065 2 −179.99775675H 5 1.08081519 4 115.60528617 3 0.01332517H 6 1.08138854 5 118.46858695 4 −179.99035155O 1 1.35530650 7 121.00849564 6 179.99594443O 15 1.43341848 1 111.24032872 7 0.00093123O 2 1.20865985 1 84.97853906 7 0.06805619

TS16a

CC 1 5.42129739C 2 1.49315014 1 44.83749656C 3 1.33976481 2 125.19362222 1 1.28052521C 4 1.44240400 3 123.32381568 2 −1.81322350C 5 1.35324636 4 128.27129208 3 −178.64729797O 1 1.32262345 6 121.40503694 5 −175.71399120H 7 0.96362806 1 110.42868995 6 1.39733618O 2 1.34929221 1 104.44756108 7 82.10557377H 9 0.96988769 2 107.53826475 1 −136.51016221H 3 1.08285670 2 114.60525735 1 178.66079710H 4 1.07950647 3 118.46196550 2 177.84175543H 5 1.08372201 4 116.28393011 3 2.07375739H 6 1.08348237 5 117.09186729 4 −178.88683775O 1 1.26803102 7 117.93748491 6 179.62342116O 15 1.38569264 1 118.29811359 7 0.79974513O 2 1.20246491 1 115.84216001 15 118.30901576

24

TS16b

CC 1 5.46748957C 2 1.47512531 1 42.48237549C 3 1.34866331 2 126.22278901 1 −2.39550227C 4 1.44034340 3 125.84037152 2 −0.89403561C 5 1.35748097 4 127.03317987 3 177.03008182O 1 1.33210853 6 120.27878428 5 173.55412758H 7 0.96405112 1 113.73151493 6 −77.90602545O 2 1.35508109 1 152.86773803 7 168.47033247H 9 0.96791141 2 107.16388324 1 176.63976675H 3 1.08059389 2 114.90610894 1 177.47370987H 4 1.08081481 3 116.74153337 2 179.08852923H 5 1.08023845 4 116.16544618 3 −3.51764449H 6 1.08178542 5 117.69600566 4 178.15734274O 1 1.27609470 7 119.18660022 6 −175.70116024O 15 1.36581640 1 119.57152190 7 −8.74724188O 2 1.20952223 1 85.09524622 15 167.47300205

TS16c

CC 1 5.56527529C 2 1.47422542 1 37.89217333C 3 1.34953347 2 130.71513971 1 −2.34613906C 4 1.43995176 3 127.63789440 2 −1.21791531C 5 1.35801996 4 126.91011991 3 177.45768921O 1 1.33224063 6 120.23966436 5 173.75751826H 7 0.96405510 1 113.72923137 6 −77.64035307O 2 1.35710226 1 77.96125157 7 −16.49368733H 9 0.96818372 2 106.48024519 1 −179.20040777H 3 1.08084861 2 111.12247022 1 177.53337725H 4 1.08104667 3 115.80544918 2 178.93678101H 5 1.07910784 4 116.95927265 3 −3.33361280H 6 1.08175858 5 117.63088146 4 178.09346853O 1 1.27614415 7 119.17356112 6 −175.61728341O 15 1.36513465 1 119.57628225 7 −8.63736783O 2 1.20756834 1 160.35901026 15 −12.16183317

25

TS16d

CC 1 5.46505574C 2 1.49359891 1 45.31642132C 3 1.33743677 2 125.31432625 1 0.60876462C 4 1.44807412 3 123.28790348 2 −2.18806438C 5 1.34485357 4 129.11154411 3 −179.43099744O 1 1.21284152 6 124.06400740 5 −179.29274605H 7 1.85110975 1 85.10794491 6 −179.98601501O 2 1.34942369 1 105.20225448 7 74.29876757H 9 0.96984417 2 107.51733589 1 −135.55887416H 3 1.08304480 2 114.46048855 1 177.99294991H 4 1.07914624 3 118.41741838 2 177.46865269H 5 1.08461874 4 115.62361419 3 0.92535194H 6 1.08094668 5 118.76164565 4 −179.67560266O 1 1.35594753 7 121.00574261 6 179.89986949O 15 1.43335324 1 111.19236696 7 0.08595290O 2 1.20229179 1 114.91254883 7 −64.49100884

26

Figure 1: IRC paths for Step 1 obtained from calculations at B3LYP/6-311+G(2df,2p) level.

27

Figure 2: IRC paths for the formation of Creigee Intermidiates (CI) from primary ozonides (POZ) obtained from calculations atB3LYP/6-311+G(2df,2p) level.

28

Figure 3: IRC paths for CI1 and CI3 obtained from calculations at B3LYP/6-311+G(2df,2p) level.

Figure 4: IRC paths for CI4 obtained from calculations at B3LYP/6-311+G(2df,2p) level.

(a) (b)

Figure 5: Transition state search by scanning through dihedral angle (a) 6 C1C2O9H10 and (b) 6 C2C1O7H8 by freezingC1-O15-O16-O17-C2 moiety at B3LYP/6-311+G(2df,2p) level.

29

Table S1: Forward (EF ) and backward (ER) energy barriers in kJ mol−1 calculated by various methods .

Cat+Oz→ POZ1 Cat+Oz→ POZ2 Cat+Oz→ POZ3Methods EF ER EF ER EF ER

PBE/6-311++G(d,p) 19.8 105.6 17.3 107.0 34.7 134.5PBE/6-311+G(2df,2p) 24.6 109.4 21.8 109.7 39.6 136.9TPSS/6-311++G(d,p) 21.8 114.9 18.9 116.7 34.9 142.1TPSS/6-311+G(2df,2p) 27.3 119.1 23.9 119.5 40.4 144.7B3LYP/6-311++G(d,p) 26.2 106.4 26.6 110.5 47.3 143.7B3LYP/6-311+G(2df,2p) 33.6 110.3 34.3 114.2 55.0 147.1B3PW91/6-311++G(d,p) 27.1 113.3 27.5 117.3 49.8 152.3B3PW91/6-311+G(2df,2p) 34.9 117.7 35.5 121.4 57.7 156.1M06-2X/6-311++G(d,p) 18.1 183.0 39.2 219.6M06-2X/6-311+G(2df,2p) 28.4 183.9 49.7 220.2M06-2X/aug-cc-pvtz 29.7 184.7 30.4 188.8 50.4 220.6wB97XD/6-311++G(d,p) 27.9 145.6 28.8 150.2 50.7 184.2wB97XD/6-311+G(2df,2p) 36.4 149.8 37.2 153.8 58.8 186.4MN15/6-311++G(d,p) 11.4 158.1 11.4 163.5 32.6 195.6MN15/6-311+G(2df,2p) 20.5 163.5 20.7 168.5 41.3 199.9MP2/6-311++G(d,p) 61.6 110.3 78.0 148.1MP2/6-311++G(2df,2p) 54.5 108.6 55.7 118.8 72.2 146.3CCSD(T)/Extrapolated// 38.5 160.2 36.5 163.2 58.5 196.5B3LYP/6-311++G(d,p)CCSD(T)/Extrapolated// 37.0 160.3 35.1 163.6 56.7 196.4B3LYP/6-311+G(2df,2p)CCSD(T)/Extrapolated// 34.9 159.7 55.7 197.8M06-2X/6-311++G(d,p)CCSD(T)/Extrapolated// 34.7 160.7 33.4 165.6 55.4 197.7M06-2X/aug-cc-pvtzCCSD(T)/Extrapolated// 35.6 160.1 34.3 163.8 56.2 196.3MN15/6-311+G(2fd,2p)CCSD(T)-F12/VDZ-F12// 45.5 151.2 45.2 155.6 64.6 187.3B3LYP/6-311++G(d,p)

30

Table S2: Optimized energies, Zero point corrections (ZPE), Thermal correction to Energy (∆E), Thermal correction to Enthalpy(∆H), Thermal correction to Gibbs Free Energy (∆G) in atomic units, total partition function (Q) and imaginary frequencies (Imω in cm−1) obtained from B3LYP/6-311+G(2df,2p) method.

Species Energy ZPE ∆E ∆H ∆G Q Im ω

Catechol −382.831561 0.108859 0.115571 0.116515 0.078392 0.1033×1015 -Ozone −225.496198 0.007328 0.010285 0.011229 −0.015776 0.4237×1011 -PR1 −608.335457 0.118010 0.128672 0.129617 0.080737 0.1394×1018 -PR2 −608.332458 0.117579 0.128666 0.129611 0.079394 0.3660×1018 -TS1 −608.316225 0.117467 0.127079 0.128023 0.083111 0.6352×1016 379.06iTS2 −608.315914 0.117402 0.126879 0.127823 0.083171 0.5562×1016 379.42iTS3 −608.307866 0.117244 0.126981 0.127926 0.082299 0.1184×1017 425.35iPOZ1 −608.360373 0.119593 0.128867 0.129811 0.085493 0.4839×1016 -TS4a −608.359960 0.119156 0.127766 0.128710 0.085695 0.2458×1016 173.09iTS4b −608.357857 0.119414 0.127931 0.128875 0.086136 0.2028×1016 274.44iPOZ2 −608.361878 0.119883 0.128855 0.129799 0.086239 0.2988×1016 -TS4c −608.357741 0.119260 0.127762 0.128707 0.086335 0.1395×1016 187.08iPOZ3 −608.366274 0.119637 0.128792 0.129736 0.085748 0.3872×1016 -TS5 −608.339077 0.117229 0.126528 0.127472 0.083565 0.3048×1016 473.24iTS6 −608.347116 0.117685 0.126600 0.127544 0.084434 0.1969×1016 452.18iTS7 −608.342870 0.117622 0.126763 0.127707 0.083755 0.3782×1016 523.23iTS8 −608.343332 0.117699 0.126664 0.127608 0.084177 0.2625×1016 469.73iCI1# −608.419493 0.118648 0.129436 0.130380 0.080868 0.2386×1018 -CI2# −608.423705 0.118706 0.129524 0.130468 0.080818 0.2675×1018 -POA1# −608.480702 0.119257 0.130119 0.131063 0.080917 0.4313×1018 -CI4# −608.415096 0.118850 0.129723 0.130667 0.080901 0.2853×1018 -TS9 −608.418804 0.118214 0.128279 0.129224 0.081316 0.9368×1017 37.57iTS10 −608.422860 0.118187 0.128333 0.129278 0.081050 0.1207×1018 42.73iTS11 −608.480335 0.118854 0.128972 0.129916 0.081419 0.1656×1018 34.43iTS12 −608.414311 0.118301 0.128477 0.129421 0.081236 0.1119×1018 39.74i

31

Table S2: Optimized energies, Zero point corrections (ZPE), Thermal correction to Energy (∆E), Thermal correction to Enthalpy(∆H), Thermal correction to Gibbs Free Energy (∆G) in atomic units, total partition function (Q) and imaginary frequencies (Imω in cm−1) obtained from B3LYP/6-311+G(2df,2p) method.


CI1a −608.427970 0.118988 0.129838 0.130782 0.080786 0.3730×1018 -CI1b −608.425479 0.118989 0.129877 0.130821 0.080616 0.4468×1018 -CI1c −608.433372 0.119237 0.130129 0.131073 0.080470 0.6785×1018 -CI1d −608.435755 0.119202 0.130078 0.131022 0.080485 0.6434×1018 -TS13a −608.419079 0.118282 0.128460 0.129404 0.081135 0.1220×1018 69.36iTS13b −608.421139 0.118004 0.128540 0.129485 0.079908 0.3334×1018 383.13iTS13c −608.427358 0.118493 0.128659 0.129603 0.081106 0.1573×1018 71.47iTS13d −608.423581 0.118019 0.128520 0.129464 0.080113 0.2727×1018 380.89iCI2a −608.435755 0.119202 0.130078 0.131022 0.080485 0.6434×1018 -CI2b −608.427970 0.118988 0.129838 0.130782 0.080786 0.3730×1018 -CI2c −608.425479 0.118989 0.129877 0.130821 0.080616 0.4468×1018 -CI2d −608.433372 0.119237 0.130129 0.131073 0.080470 0.6785×1018 -TS14a −608.423581 0.118019 0.128520 0.129464 0.080113 0.2727×1018 380.89iTS14b −608.419079 0.118282 0.128460 0.129404 0.081135 0.1220×1018 69.36iTS14c −608.421139 0.118004 0.128540 0.129485 0.079908 0.3334×1018 383.13iTS14d −608.427358 0.118493 0.128659 0.129603 0.081106 0.1573×1018 71.47iPOA1a −608.491392 0.120004 0.130849 0.131794 0.080998 0.8739×1018 -POA1b −608.494070 0.119986 0.130795 0.131739 0.081175 0.7109×1018 -TS15 −608.485495 0.119246 0.129351 0.130295 0.081792 0.1688×1018 70.76iCI4a −608.427411 0.119302 0.130277 0.131222 0.079050 0.3272×1019 -CI4b −608.430550 0.119328 0.130264 0.131208 0.079331 0.2496×1019 -POA2a −608.491392 0.120004 0.130849 0.131794 0.080998 0.8739×1018 -POA2b −608.494070 0.119986 0.130795 0.131739 0.081175 0.7109×1018 -TS16a −608.421109 0.118566 0.128792 0.129736 0.080897 0.2123×1018 72.56iTS16b −608.422683 0.118029 0.128600 0.129544 0.079785 0.3899×1018 541.04iTS16c −608.419771 0.118037 0.128642 0.129586 0.079618 0.4692×1018 536.33iTS16d −608.485495 0.119246 0.129351 0.130295 0.081792 0.1688×1018 70.76i

32

Table S3: Optimized energies, Zero point corrections (ZPE), Thermal correction to Energy (∆E), Thermal correction to Enthalpy(∆H), Thermal correction to Gibbs Free Energy (∆G) in atomic units, total partition function (Q) and imaginary frequencies (Imω in cm−1) obtained from MN15/6-311+G(2df,2p) method.


Catechol −382.389540 0.109560 0.116255 0.117200 0.079124 0.9989×1014 -Ozone −225.269600 0.007897 0.010837 0.011781 −0.015168 0.4068×1011 -PR1 −607.670870 0.118503 0.129288 0.130233 0.081468 0.1083×1018 -PR2 −607.668244 0.118180 0.129244 0.130188 0.080424 0.2326×1018 -

TS1 −607.652506 0.118617 0.128307 0.129251 0.084062 0.7841×1016 411.44iTS2 −607.652445 0.118642 0.128181 0.129125 0.084253 0.6573×1016 409.62iTS3 −607.644579 0.118641 0.128283 0.129227 0.083839 0.1018×1017 461.55iPOZ1 −607.717441 0.121291 0.130576 0.131520 0.086839 0.7034×1016

TS4a −607.717048 0.120985 0.129510 0.130454 0.087432 0.2712×1016 150.96iTS4b −607.715456 0.121263 0.129690 0.130634 0.087979 0.2039×1016 234.92iPOZ2 −607.719645 0.121669 0.130575 0.131520 0.087982 0.3126×1016

TS4c −607.715925 0.121159 0.129511 0.130455 0.088405 0.1163×1016 179.31iPOZ3 −607.723556 0.121498 0.130543 0.131488 0.087685 0.3571×1016 -TS5 −607.686407 0.118603 0.127913 0.128857 0.084992 0.2885×1016 551.76iTS6 −607.694182 0.119217 0.128054 0.128998 0.086115 0.1681×1016 535.41iTS7 −607.689329 0.119259 0.128206 0.129150 0.085800 0.2455×1016 646.26iTS8 −607.685779 0.119054 0.128109 0.129053 0.085290 0.3391×1016 540.72iCI1# −607.760129 0.119725 0.130480 0.131424 0.082102 0.2020×1018 -CI2# −607.763701 0.119864 0.130605 0.131549 0.082484 0.1563×1018 -POA1# −607.823250 0.120686 0.131433 0.132377 0.082954 0.2267×1018 -CI4# −607.754395 0.120064 0.130802 0.131746 0.083031 0.1081×1018 -TS9 −607.761326 0.119256 0.129185 0.130129 0.083465 0.2903×1017 66.61iTS10 −607.761857 0.119188 0.129354 0.130298 0.081908 0.1405×1018 48.35iTS11 −607.821618 0.120090 0.130199 0.131143 0.082634 0.1691×1018 54.36iTS12 −607.752020 0.119306 0.129505 0.130449 0.082106 0.1290×1018 50.48i

33

Table S3: Optimized energies, Zero point corrections (ZPE), Thermal correction to Energy (∆E), Thermal correction to Enthalpy(∆H), Thermal correction to Gibbs Free Energy (∆G) in atomic units, total partition function (Q) and imaginary frequencies (Imω in cm−1) obtained from MN15/6-311+G(2df,2p) method.


CI1a −607.765513 0.120061 0.130902 0.131846 0.081761 0.4138×1018 -CI1b −607.762828 0.120082 0.130951 0.131895 0.081641 0.4803×1018 -CI1c −607.768500 0.120274 0.131233 0.132177 0.080786 0.1457×1019 -CI1d −607.771049 0.120241 0.131177 0.132121 0.080817 0.1361×1019 -TS13a −607.756814 0.119364 0.129526 0.130471 0.082219 0.1218×1018 71.59iTS13b −607.756164 0.119006 0.129606 0.130550 0.080591 0.4674×1018 416.65iTS13c −607.763348 0.119558 0.129757 0.130702 0.081922 0.2048×1018 71.43iTS13d −607.758790 0.118981 0.129552 0.130496 0.080705 0.4037×1018 416.98iCI2a −607.771049 0.120241 0.131177 0.132121 0.080817 0.1361×1019 -CI2b −607.765513 0.120061 0.130902 0.131846 0.081761 0.4138×1018 -CI2c −607.762828 0.120082 0.130951 0.131895 0.081641 0.4803×1018 -CI2d −607.768500 0.120274 0.131233 0.132177 0.080786 0.1457×1019 -TS14a −607.758790 0.118981 0.129552 0.130496 0.080705 0.4037×1018 416.98iTS14b −607.756814 0.119364 0.129526 0.130471 0.082219 0.1218×1018 71.59iTS14c −607.756164 0.119006 0.129606 0.130550 0.080591 0.4674×1018 416.65iTS14d −607.763348 0.119558 0.129757 0.130702 0.081922 0.2048×1018 71.43iPOA1a −607.829611 0.121247 0.132113 0.133057 0.082057 0.1063×1019 -POA1b −607.832497 0.121231 0.132071 0.133015 0.082082 0.1017×1019 -TS15 −607.824390 0.120490 0.130607 0.131551 0.082925 0.1901×1018 70.95iCI4a −607.761549 0.120411 0.131337 0.132281 0.081428 0.8534×1018 -CI4b −607.764924 0.120427 0.131316 0.132260 0.081594 0.7272×1018 -POA2a −607.829611 0.121247 0.132113 0.133057 0.082057 0.1063×1019 -POA2b −607.832497 0.121231 0.132071 0.133015 0.082082 0.1017×1019 -TS16a −607.756132 0.119670 0.129899 0.130843 0.081966 0.2201×1018 72.26iTS16b −607.757097 0.119036 0.129655 0.130599 0.080542 0.5079×1018 547.49iTS16c −607.753952 0.119029 0.129682 0.130626 0.080380 0.5991×1018 543.74iTS16d −607.824390 0.120490 0.130607 0.131551 0.082925 0.1901×1018 70.95i

34

Table S4: Energies (in au) calculated at CCSD(T)/cc-pVXZ (X=2,3) and the corresponding T1 diagnostics values and theCCSD(T)/Extrapolated limit for the structure obtained from B3LYP/6-311+G(2df,2p) method.

Species CCSD(T)/cc-pVDZ T1 CCSD(T)/cc-pVTZ T1 CCSD(T)/ExtrapolatedCatechol −381.684879 0.012 −382.067310 0.012 −382.228334Ozone −224.907900 0.026 −225.131806 0.026 −225.226082PR1 −606.602838 0.019 −607.206785 0.019 −607.461078PR2 −606.597906 0.019 −607.203926 0.018 −607.459093TS1 −606.578363 0.030 −607.185837 0.028 −607.441615TS2 −606.579891 0.030 −607.186736 0.028 −607.442250TS3 −606.571483 0.029 −607.178342 0.028 −607.433862POZ1 −606.637071 0.015 −607.247684 0.015 −607.504785TS4a −606.637447 0.015 −607.247318 0.015 −607.504106TS4b −606.635567 0.015 −607.245788 0.015 −607.502723POZ2 −606.640595 0.015 −607.250329 0.015 −607.507059TS4c −606.637316 0.014 −607.246409 0.014 −607.502870POZ3 −606.644779 0.015 −607.254387 0.015 −607.511064TS5 −606.616456 0.018 −607.222671 0.018 −607.477919TS6 −606.627056 0.017 −607.231467 0.018 −607.485956TS7 −606.619604 0.019 −607.225500 0.019 −607.480614TS8 −606.619973 0.017 −607.224413 0.017 −607.478914CI1# −606.678349 0.028 −607.285183 0.026 −607.540692CI2# −606.681679 0.027 −607.287996 0.025 −607.543287POA1# −606.750213 0.017 −607.354632 0.016 −607.609124CI4# −606.671151 0.016 −607.279567 0.027 −607.535743TS9 −606.676531 0.027 −607.284290 0.025 −607.540189TS10 −606.679631 0.026 −607.286683 0.024 −607.542284TS11 −606.748778 0.017 −607.353644 0.016 −607.608325TS12 −606.669314 0.029 −607.278116 0.027 −607.534454CI1a −606.684438 0.029 −607.290711 0.026 −607.545984TS13d −606.680914 0.032 −607.286007 0.030 −607.540784CI1d −606.691064 0.028 −607.296323 0.026 −607.551168CI2a −606.691064 0.028 −607.296323 0.026 −607.551168POA1a −606.758352 0.017 −607.361737 0.017 −607.615794TS15 −606.751685 0.017 −607.356570 0.017 −607.611258POA1b −606.761423 0.017 −607.364586 0.017 −607.618549CI4a −606.680742 0.032 −607.287654 0.029 −607.543196CI4b −606.684131 0.032 −607.290870 0.029 −607.546340POA2a −606.758352 0.017 −607.361737 0.017 −607.615794POA2b −606.761423 0.017 −607.364586 0.017 −607.618549TS16a −606.673652 0.031 −607.282225 0.028 −607.538466TS16b −606.677828 0.034 −607.283891 0.031 −607.539075TS16c −606.674662 0.034 −607.280901 0.031 −607.536160TS16d −606.751685 0.017 −607.356570 0.017 −607.611258

35

Table S5: Zero-point corrected relative energies (kJ/mol) of the reactants, pre-reactive complexes, transitionstates and products calculated by B3LYP/6-311+G(2df,2p), M06-2X/6-311+G(2df,2p), MN15/6-311+G(2df,2p) andCCSD(T)/Extrapolated//B3LYP/6-311+G(2df,2p) methods.

Species B3LYP M06-2X MN15 CCSD(T) Species B3LYP M06-2X MN15 CCSD(T)Catechol+Ozone 0.0 0.0 0.0 0.0 TS9 −233.7 −272.8 −263.6 −219.9PR1 −15.4 −23.0 −28.1 −12.7 TS10 −244.4 −280.7 −265.1 −225.5PR2 −8.7 −18.4 −22.0 −8.6 TS11 −393.6 −442.1 −419.7 −397.1TS1 33.6 28.4 20.5 37.0 TS12 −221.7 −255.1 −239.0 −204.6TS2 34.3 - 20.7 35.1 CI1a −255.7 −284.6 −272.5 −233.1TS3 55.0 49.7 41.3 56.7 TS13d −246.8 −270.0 −257.6 −221.9POZ1 −76.7 −155.6 −143.0 −123.3 CI1d −275.6 −300.0 −286.5 −246.1TS4a −76.7 −156.0 −142.8 −122.7 CI2a −275.6 −300.0 −286.5 −246.1TS4b −70.5 −151.2 −137.9 −118.4 POA1a −419.6 −458.6 −437.6 −413.7POZ2 −79.9 −159.1 −147.8 −128.5 TS15 −406.1 −447.3 −425.9 −403.8TS4c −70.7 −151.5 −139.4 −119.1 POA1b −426.7 −465.8 −445.2 −421.0POZ3 −92.1 −170.6 −158.5 −139.7 CI4a −253.5 −274.7 −261.1 −224.9TS5 −27.0 −67.1 −68.6 −59.0 CI4b −261.6 −283.2 −269.9 −233.1TS6 −46.9 −85.7 −87.4 −78.9 POA2a −419.6 −458.6 −437.6 −413.7TS7 −35.9 −73.1 −74.5 −65.0 POA2b −426.7 −465.8 −445.2 −421.0TS8 −36.9 −68.0 −65.7 −60.3 TS16a −238.9 −263.1 −248.8 −214.4CI1# −234.4 −273.7 −259.2 −220.1 TS16b −244.4 −265.5 −253.0 −217.4CI2# −245.3 −284.2 −268.2 −226.7 TS16c −236.7 −257.6 −244.8 −209.8POA1# −393.5 −445.7 −422.4 −398.1 TS16d −406.1 −447.3 −425.9 −403.8CI4# −222.3 −260.0 −243.3 −206.5

36

Table S6: Forward energy barriers (EF ), reverse energy barriers (ER) in kJmol−1 calculated by B3LYP/6-311++G(2df,2p), M06-2X/6-311+G(2df,2p), MN15/6-311++G(2df,2p) and CCSD(T)/Extrapolated//B3LYP/6-311++G(2df,2p) methods.

B3LYP M06-2X MN15 CCSD(T)Reaction EF ER EF ER EF ER EF ER

Cat+Oz→ TS1→ POZ1 33.6 110.3 28.4 183.9 20.5 163.5 37.0 160.3Cat+Oz→ TS2→ POZ2 34.3 114.2 - - 20.7 168.5 35.1 163.6Cat+Oz→ TS3→ POZ3 55.0 147.1 49.7 220.2 41.3 199.9 56.7 196.4POZ1→ TS4a→ POZ2 −0.1 3.1 −0.4 3.1 0.2 5.0 0.6 5.8POZ1→ TS4b→ POZ2i 6.1 9.3 4.3 7.8 5.1 9.9 4.9 10.1POZ2→ TS4c→ POZ3 9.2 21.4 7.5 19.1 8.4 19.1 9.4 20.5POZ1→ TS5→ CI1# 49.7 207.4 88.5 206.6 74.4 190.6 64.3 161.1POZ2→ TS6→ CI2# 33.0 198.4 73.4 198.6 60.4 180.8 49.6 147.8POZ3→ TS7→ POA1# 56.2 357.6 97.5 372.6 84.0 347.9 74.7 333.1POZ3→ TS8→ CI4# 55.1 185.4 102.6 192.0 92.8 177.5 79.3 146.2CI1#→ TS9→ CI1a 0.7 22.0 0.9 11.8 −4.4 8.9 0.2 13.2CI2#→ TS10→ CI2a 0.9 31.2 3.5 19.2 3.1 21.4 1.3 20.7POA1#→ TS11→ CI3ha −0.1 26.0 3.6 16.5 2.7 17.9 1.0 16.6CI4#→ TS12→ CI4a 0.6 31.8 4.8 19.6 4.3 22.1 1.9 20.3CI1a→ TS13d→ CI1d 9.0 28.9 14.6 30.0 14.8 28.9 11.1 24.2POA1a→ TS15→ POA1b 13.5 20.6 11.3 18.5 11.7 19.3 9.9 17.2CI4a→ TS16a→ CI4b 14.6 22.8 11.6 20.1 12.3 21.1 10.5 18.7CI4b→ TS16b→ POA2b 17.2 182.3 17.7 200.3 16.9 192.2 15.7 203.5CI4a→ TS16c→ POA2a 16.7 182.9 17.1 201.0 16.3 192.8 15.1 203.9POA2a→ TS16d→ POA2b 13.5 20.6 11.3 18.5 11.7 19.3 9.9 17.2

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VLFV 7KLVMRXUQDOLV WKH2ZQHU6RFLHWLHV · 2019. 5. 16. · h 6 1.08121203 5 122.37491736 4 178.63165220 o 1 1.45594338 7 107.50452309 6 119.08205659 o 15 1.42273678 1 102.90484263 7