Two-photon excitation of conjugated molecules in solution: Spectroscopy and excited-state dynamics

Elles, Christopher G.

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https://hdl.handle.net/2142/97202 Copy

Description

Title

Two-photon excitation of conjugated molecules in solution: Spectroscopy and excited-state dynamics

Author(s)

Elles, Christopher G.

Contributor(s)

• Krylov, Anna
• de Wergifosse, Marc
• Houk, Amanda L.

Issue Date

2017-06-21

Keyword(s)

Multiple potential energy surfaces

Abstract

We examine the two-photon absorption (2PA) spectroscopy and ultrafast excited-state dynamics of several conjugated molecules in solution. By controlling the relative wavelength and polarization of the two photons, the 2PA measurements provide a more sensitive means of probing the electronic structure of a molecule compared with traditional linear absorption spectra. We compare experimental spectra of trans-stilbene, cis-stilbene, and phenanthrene in solution with the calculated spectra of the isolated molecules using EOM-EE-CCSD. The calculated spectra show good agreement with the low-energy region of the experimental spectra (below ~6 eV) after suppressing transitions with strong Rydberg character and accounting for solvent and method-dependent shifts of the valence transitions. We also monitor the excited state dynamics following two-photon excitation to high-lying valence states of trans-stilbene up to 6.5 eV. The initially excited states rapidly relax to the lowest singlet excited state and then follow the same reaction path as observed following direct one-photon excitation to the lowest absorption band at 4.0 eV.

Publisher

International Symposium on Molecular Spectroscopy

Type of Resource

text

Language

eng

Permalink

http://hdl.handle.net/2142/97202

DOI

https://doi.org/10.15278/isms.2017.WB10

Copyright and License Information

Copyright 2017 Christopher G. Elles

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