Journal
PHYSICAL REVIEW LETTERS
Volume 120, Issue 22, Pages -Publisher
AMER PHYSICAL SOC
DOI: 10.1103/PhysRevLett.120.223002
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Funding
- Australian Research Council [DP150101427, DP160100474, FT130101304]
- Microsoft Azure Research Award
- Australian government
- Austrian Science Fund (FWF) through a Schrodinger Fellowship [J4013-N36]
- Austrian Science Fund (FWF) [J4013] Funding Source: Austrian Science Fund (FWF)
- Australian Research Council [FT130101304] Funding Source: Australian Research Council
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The shapes of many molecules can be transformed by light or heat. Here we investigate collision-and photon-induced interconversions of EE, EZ, and ZZ isomers of the isolated Congo red (CR) dianion, a double molecular switch containing two -N=N- azo groups, each of which can have the E or Z configuration. We find that collisional activation of CR dianions drives a one-way ZZ -> EZ -> EE cascade towards the lowest-energy isomer, whereas the absorption of a single photon over the 270-600 nm range can switch either azo group from E to Z or Z to E, driving the CR dianion to lower-or higher-energy forms. The experimental results, which are interpreted with the aid of calculated statistical isomerization rates, indicate that photoisomerization of CR in the gas phase involves a passage through conical intersection seams linking the excited and ground state potential energy surfaces rather than through isomerization on the ground state potential energy surface following internal conversion.
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