Ab Initio Study of Potential Ultrafast Internal Conversio

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

Implications for Sunscreens
Tolga N. V. Karsili,* ,, Barbara Marchetti, Michael N. R. Ashfold,* , and
Wolfgang Domcke
School of Chemistry, University of Bristol, Bristol BS8 1TS, United Kingdo
m
Department of Chemistry, Technische Universitat Munchen, Lichtenbergstra
sse 4, 85747 Garching, Germany
: J. Phys. Chem. A. 2014, 118, 1199912010
: 2015/3/2
: 402
:
:

Introduction

Sunscreen

Caffeic / Ferulic acid

Internal Conversion
(IC)

Oxybenzone

Possible IC pathway for phenol

(O-H bond extension)
MRCI/aug-cc-pVDZ //CASSCF(10,9)/aug-cc-pVDZ

Conical intersection
(CI)

Vieuxmaire, O.; Lan, Z.; Sobolewski, A. L.; Domcke, W. J. Chem.

Phys. 2008, 129, 224307.

Possible IC pathway for Benzene

(Ring centered out-of plane deformation )

MC-SCF/4-31
The structure of (i)*

MC-SCF/4-31G
Palmer, I. J.; Ragazos, I. N.; Bernardi, F.;
Olivucci, M.; Robb, M. A. J. Am. Chem.
Soc. 1993, 115, 673.

Possible IC pathway for Stilbene

SA-2-CAS(2/2)
// 6-31G**
(E/Z photoisomerism)

E(trans) form

Z(cis) form

Quenneville, J.; Martnez, T. J. J. Phys.

Chem. A. 2003, 107, 829.

Possible IC pathway for Adenosine

(Electron driven hydrogen atom transfer)
)

ADC(2)/cc-pVDZ
//MP2/cc-pVDZ

Tuna, D.; Sobolewski, A. L.; Domcke, W. J. Phys. Chem. A. 2013, 118,

6
122.

Motivation
Oxybenzone (OB) Cafferic acid
(CA) Ferulic acid (FA) Internal Conv
ersion (IC)

Goal
Possible Internal Conversion Pathways

IC
CA FA OB
O-H/O-CH3 bond extension (For CA and FA)
Ring centered out-of plane deformation and E/Z photoisomerism
(For CA, FA and OB)
Electron driven hydrogen atom transfer (For OB)

Strategy
Possible Internal Conversion Pathways
I
C
CA FA OB
: EOM-CCSD/cc-pVDZ, TD-CAMB3LYP/cc-pVDZ CASPT2/cc-pVDZ

O-H/O-CH3 bond extension (For CA and FA)

: MP2/aug-cc-pVDZ CAMB3LYP/aug-cc-pVDZ
O-H/O-CH3 bond extension : CASPT2(12,11)/cc-pVDZ//MP2/ aug-cc-pV
DZ

Ring centered out-of plane deformation and E/Z photoisomerism (For CA, FA an
d OB)
CA FA : CASPT2(14,12 for CA or 12,11 for FA)/cc-pVDZ//CASSCF
(6,6)/6-31G(d)
OB : CASPT2(10,8)/cc-pVDZ//CASSCF(10,8)/ 3-21G

Electron driven hydrogen atom transfer (For OB)

: CAMB3LYP/cc-pVDZ

Blue : CAMB3LYP/aug-cc-pVDZ
Pink : MP2/aug-cc-pVDZ Unit :eV

Cafferic /
Ferulic acid
(CA /FA)

Results and Discussion

0 (0)

0.18

Oxybenzone
(OB)

0.22
(0.20)

0.027
(0.017)

0.36
(0.34)

0.53

0.46

10

Cafferic acid (CA)

State

EXP

11*b

4.19b(0.0924c)

4.15b(0.3294c)

4.19b(0.1635c)

4.12b(0.2308c)

3.97 and 4.35

11n*b

4.81b(0.0003c)

4.99b(0.0008c)

4.91b(0.0002c)

4.59b(0.0001c)

21*b

4.97b(0.4566c)

4.66b(0.2344c) 4.92b(0.5124c)
Ferulic acid (FA)

4.33b(0.4088c)

State

11*b

4.19b(0.2746c)

4.15b(0.3831c)

4.19b(0.2966c)

4.12b(0.0687c)

11n*b

4.80b(0.0003c)

4.99b(0.0001c)

4.91b(0.0001c)

4.59b(0.0001c)

21*b

4.90b(0.3816c)

4.66b(0.1727c)

4.92b(0.3288c)

4.33b(0.4848c)

Oxybenzone (OB)

State

EXP

11*b

3.36b
4.19d(0.0195)

3.85d(0.0015)

3.89d(0.0044)

3.75
and 4.35

1 n*

3.72
4.26d(0.1858)

4.72 (0.1939)

4.69 (0.2081)

21*b

4.30b
4.82d(0.2791)

5.12d(0.0512)

5.11d(0.0369)

CASPT2/cc-pVDZ

EOM-CCSD/cc-pVDZ

TD-CAMB3LYP/ccpVDZ
d

Unit : eV

11

EOM-CCSD/cc-pVDZ

TD-CAMB3LYP/cc-pVDZ

12

O-H/O-CH3 bond extension of CA and

CI strucutre
FA

CASPT2(12,11)/cc-pVDZ//MP2/ aug-cc-pVDZ

13

Ring centered out-of plane deformation of C

A and
FA
CI strucutre

E form

E form

CASPT2(12,11 or 14,12)/cc-pVDZ//CASSCF/6-31G(d) for CI structures

CASPT2(12,11 or 14,12)/cc-pVDZ//MP2/ aug-cc-pVDZ for ground state structures

14

Ring centered out-of plane deformation of O

CI strucutre
B E form

CASPT2(10,8)/cc-pVDZ//CASSCF(10,8)/ 3-21G for CI structures

CASPT2(10,8)/cc-pVDZ//MP2/ cc-pVDZ for ground state structures

15

E/Z photoisomerism of CA and FA

E form

Z form

E form

Z form

CI strucutre
CASPT2(12,11 or 14,12)/cc-pVDZ//CASSCF(6,6)/6-31G(d) for CI structures
CASPT2(12,11 or 14,12)/cc-pVDZ//MP2/ aug-cc-pVDZ for ground state structures

16

Electron driven hydrogen atom transfer

CI strucutre
of OB
CI strucutre
CAMB3LYP/cc-pVDZ
S1 orbitals
RO-H= 1
RO-H= 2

17

Conclusion
1. CA FA O-H / O-CH3
11* CI-11*/ 11*
11* 11*/S0 ( )

2. CA FA OB S1 (S1 for CA and FA : 11*

S1 for OB and FA : 11n* )
(Ring centered out-of plane deformation)
CI-S1/S0
3. CA FA E/Z photoisomerism
IC CI-21*/ S0
E-form Z-form

18

4. OB electron driven hydrogen atom transf

er OB 11n* state
CI- 11n*/S0

IC
5. CA FA IC O-H / O-CH3

OB electron driv
en hydrogen atom transfer
hydrogen atom tr
ansfer OB IC
19