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Ab Initio Study of Potential Ultrafast Internal Conversio

n Routes in Oxybenzone, Caffeic Acid, and Ferulic Acid:

Imlications for Sunscreens

Tolga N. V. Karsili,* ,, Barbara Marchetti, Michael N. R. Ashfold,* , and

Wolfgang Doc!e

"chool of #heistr$, %ni&ersit$ of Bristol, Bristol B"' (T", %nited Kingdo

De)artent of #heistr$, Technische %ni&ersitt M+nchen, ichtenbergstrasse -, '/-/ 0arching, 0eran$

1 J. Phys. Chem. A.!"#$, 118, ((2223(45(5

1 45(6764

1 -54 1

1

(

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Introduction

Caffeic % Ferulic acid

Oxybenzone

"8nscreen

Internal Conversion

&IC' 4

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9ossible :# )ath;a$ for )henol? bond e@tension

Vieuxmaire, O.; Lan, Z.; Sobolewski, A. L.; Domcke, W.J. Chem.Ph s.2008 129 22430.

7

Conical intersection

&CI'(RCI%au)*cc*+- %%CASSCF",.'%au)*cc*+-

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9ossible :# )ath;a$ for Beneneof)lane deforation

M#>"#C6->7(/0e structure of &i'1

(C*SCF%$*2#3

!almer, ". #.; $a%a&os, ". '.; (ernar)i, *.;Oli+ucci, .; $obb, . A.J. Am. Chem.

Soc.1993, 115, -3. -

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9ossible :# )ath;a$ for "tilbene

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9ossible :# )ath;a$ for Adenosine

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Moti&ation

=@$benone

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0oal

9ossible :nternal #on&ersion 9ath;a$s

'()*+,-./0#1234526789:;?@9# :#/0

#A CA3 =B -.67#ABCD

=>?6=>#?7bond e@tension of )lane deforation and 6E )hotoisoeris

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"trateg$ 9ossible :nternal #on&ersion 9ath;a$s

'(+,-./0)*1234526789:;?@9#:#/0 #ACA3=B#ABCD

)*459 1 =M>##"D6cc>)VDE, TD>#AMB7G96cc>)VDE 3 #A"9T46cc>)VDE

=>?6=>#?7bond e@tension cc>)VDE#AMB7G96a8g>cc>)VDE

=>?6=>#?7bond e@tension89:;)* 1 #A"9T4)VDE66M946 a8g>cc>)V

DE

Ring centered o8t>of )lane deforation and 6E )hotoisoeris 4(0

lectron dri&en h$drogen ato transfer )VDE 2

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Res8lts and Disc8ssion

"&"'

"6!!

&"6!"'

"6"!7

&"6"#7'"625

&"62$'

"6#8

" "692 "6$5

Cafferic %

Ferulic acid

&CA %FA'

Oxybenzone

&O'

lue : CA(2;

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Cafferic acid &CA'

State A B # D 4>P

##??1b -.(2b

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4O(*CCS%cc*+- /*CA(2;

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=>?6=>#?7bond e@tension of #A and

CA

CASP/!!,##'%cc*+-%%(P!% au)*cc*+- (7

CI strucutre

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Ring centered o8t>of )lane deforation of #

A and CA

CASP/!!,## or #$,#!'%cc*+-%%CASSCF%5*2#3&d' for CI structures

CASP/!!,## or #$,#!'%cc*+-%%(P!% au)*cc*+- for )round state structures

4 form 4 form

(-

CI strucutre

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Ring centered o8t>of )lane deforation of =

B

CASP/!",8'%cc*+-%%CASSCF",8'% 2*!#3 for CI structures

CASP/!",8'%cc*+-%%(P!% cc*+- for )round state structures

4 form

(

CI strucutre

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6E )hotoisoeris of #A and CA

4 form - form 4 form - form

CASP/!!,## or #$,#!'%cc*+-%%CASSCF&5,5'%5*2#3&d' for CI structures

CASP/!!,## or #$,#!'%cc*+-%%(P!% au)*cc*+- for )round state structures(F

CI strucutre

l d i h d f

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lectron dri&en h$drogen ato transfer

of =B CA(2;

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#oncl8sion

(. #A 3 CA HIC45J'(KL =>? 6 =>#?7M#/0((HH*6 ((HI* EFP ((HI* 452 ((HI*6"5EF < QR J 12for @9kl.mWX&

('

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4. no =B @!]^ electron dri&en h$drogen ato transfer #/0< =B pH45Z ((nH*state