Ultrafast internal conversion and photochromism in gas-phase salicylideneaniline

Author:

Silfies Myles C.1ORCID,Mehmood Arshad23ORCID,Kowzan Grzegorz24ORCID,Hohenstein Edward G.5ORCID,Levine Benjamin G.23ORCID,Allison Thomas K.12ORCID

Affiliation:

1. Department of Physics and Astronomy, Stony Brook University 1 , Stony Brook, New York 11794, USA

2. Department of Chemistry, Stony Brook University 2 , Stony Brook, New York 11794, USA

3. Institute for Advanced Computational Science, Stony Brook University 3 , Stony Brook, New York 11794, USA

4. Institute of Physics, Faculty of Physics, Astronomy and Informatics, Nicolaus Copernicus University in Toruń 4 , ul. Grudziadzka 5, 87-100 Toruń, Poland

5. QC Ware Corporation 5 , Palo Alto, California 94301, USA

Abstract

Salicylideneaniline (SA) is an archetypal system for excited-state intramolecular proton transfer (ESIPT) in non-planar systems. Multiple channels for relaxation involving both the keto and enol forms have been proposed after excitation to S1 with near-UV light. Here, we present transient absorption measurements of hot gas-phase SA, jet-cooled SA, and SA in Ar clusters using cavity-enhanced transient absorption spectroscopy (CE-TAS). Assignment of the spectra is aided by simulated TAS spectra, computed by applying time-dependent complete active space configuration interaction (TD-CASCI) to structures drawn from nonadiabatic molecular dynamics simulations. We find prompt ESIPT in all conditions followed by the rapid generation of the trans keto metastable photochrome state and fluorescent keto state in parallel. Increasing the internal energy increases the photochrome yield and decreases the fluorescent yield and fluorescent state lifetime observed in TAS. In Ar clusters, internal conversion of SA is severely hindered, but the photochrome yield is unchanged. Taken together, these results are consistent with the photochrome being produced via the vibrationally excited keto population after ESIPT.

Funder

National Science Foundation

American Chemical Society Petroleum Research Fund

Air Force Office of Scientific Research

Stony Brook University

Institute for Advanced Computational Science, Stony Brook University

HORIZON EUROPE Marie Sklodowska-Curie Actions

Publisher

AIP Publishing

Subject

Physical and Theoretical Chemistry,General Physics and Astronomy

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