Fast photodynamics of azobenzene probed by scanning excited-state potential energy surfaces using slow spectroscopy

Eric M. M. Tan, Saeed Amirjalayer, Szymon Smolarek, Alexander Vdovin, Francesco Zerbetto and Wybren Jan Buma ()
Additional contact information
Eric M. M. Tan: Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam
Saeed Amirjalayer: Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam
Szymon Smolarek: Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam
Alexander Vdovin: Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam
Francesco Zerbetto: Università di Bologna
Wybren Jan Buma: Van ’t Hoff Institute for Molecular Sciences, University of Amsterdam

Nature Communications, 2015, vol. 6, issue 1, 1-7

Abstract: Abstract Azobenzene, a versatile and polymorphic molecule, has been extensively and successfully used for photoswitching applications. The debate over its photoisomerization mechanism leveraged on the computational scrutiny with ever-increasing levels of theory. However, the most resolved absorption spectrum for the transition to S1(nπ*) has not followed the computational advances and is more than half a century old. Here, using jet-cooled molecular beam and multiphoton ionization techniques we report the first high-resolution spectra of S1(nπ*) and S2(ππ*). The photophysical characterization reveals directly the structural changes upon excitation and the timescales of dynamical processes. For S1(nπ*), we find that changes in the hybridization of the nitrogen atoms are the driving force that triggers isomerization. In combination with quantum chemical calculations we conclude that photoisomerization occurs along an inversion-assisted torsional pathway with a barrier of ~2 kcal mol−1. This methodology can be extended to photoresponsive molecular systems so far deemed non-accessible to high-resolution spectroscopy.

Date: 2015
References: Add references at CitEc
Citations:

Downloads: (external link)
https://www.nature.com/articles/ncomms6860 Abstract (text/html)

Related works:
This item may be available elsewhere in EconPapers: Search for items with the same title.

Export reference: BibTeX RIS (EndNote, ProCite, RefMan) HTML/Text

Persistent link: https://EconPapers.repec.org/RePEc:nat:natcom:v:6:y:2015:i:1:d:10.1038_ncomms6860

Ordering information: This journal article can be ordered from
https://www.nature.com/ncomms/

DOI: 10.1038/ncomms6860

Access Statistics for this article

Nature Communications is currently edited by Nathalie Le Bot, Enda Bergin and Fiona Gillespie

More articles in Nature Communications from Nature
Bibliographic data for series maintained by Sonal Shukla () and Springer Nature Abstracting and Indexing ().