Photoisomerization of Self-Assembled Monolayers of Azobiphenyls: Simulations Highlight the Role of Packing and Defects
Journal article, 2016

We present surface hopping simulations of the photodynamics of self-assembled monolayers (SAMs) of 4'-(biphenyl-4-ylazo)-biphenyl-4-thiol (ABPT) on Au(111). We show that trans -> cis photoisomerization is suppressed because of steric hindrance in a well-ordered SAM. Photoisomerization is instead viable in the presence of defects. Two particularly important defects are the boundaries between domains of trans-ABPT molecules leaning in different directions (a line defect) and single cis molecules embedded in a SAM of trans (a point defect). Our findings explain the cooperative behavior observed during the photoisomerization of a trans-ABPT SAM, leading to large domains of pure cis and trans isomers. The line and point defects are predicted to produce different patterns of cis-ABPT molecules during the early stages of the photoconversion.

Author

Valentina Cantatore

Chalmers, Chemistry and Chemical Engineering, Energy and Material

G. Granucci

University of Pisa

G. Rousseau

EPITECH-France

University of Paris-Sud

G. Padula

University of Pisa

M. Persico

University of Pisa

Journal of Physical Chemistry A

1089-5639 (ISSN) 1520-5215 (eISSN)

Vol. 7 19 4027-4031

Subject Categories

Chemical Sciences

DOI

10.1021/acs.jpclett.6b02018

More information

Latest update

8/1/2018 1