Photoisomerization dynamics of trans-trans, cis-trans, and cis-cis diphenylbutadiene from broadband transient absorption spectroscopy and calculations

The Journal of Chemical Physics
O A KrohnS A Kovalenko

Abstract

The photoisomerization path and dynamics of trans-trans (ttD), cis-trans (ctD), and cis-cis (ccD) 1,4-diphenyl-1,3-butadiene (DPB) in solution are studied with broadband transient absorption (TA) spectroscopy and quantum chemical calculations. For ttD in n-hexane, 2-photon-excited TA spectra indicate that the 2Ag state is located above 1-photon allowed 1Bu (S1) by ∼1000 cm-1. Following S0 → S1 optical excitation, the isomerization occurs via torsion about a butadiene double bond to perpendicular molecular configuration P. The P-state is detected in ccD with an excited-state absorption band at 390 nm. This P-band develops during S1 → P half-torsion with time of 0.15 ps, followed further by P → S0 half-torsion and simultaneous decay with 1.6 ps in acetonitrile and 5 ps in n-hexane. In addition, two oscillation cycles between P and S1 population are observed before equilibration in n-hexane. For ctD, an indication of rising and decaying P is found in acetonitrile. The vast majority of ctD species photoisomerizes to ttD and not to ccD, in agreement a with calculated low torsional barrier about the cis double bond and high barrier about the trans double bond. Photoisomerization yield Y and time τi depend drastically on the solvent p...Continue Reading

References

Jul 1, 1983·Proceedings of the National Academy of Sciences of the United States of America·L A HeimbrookT A Spiglanin
May 1, 1948·Journal of the American Chemical Society·J H PINCKARDL ZECHMEISTER
Mar 1, 2011·The Journal of Physical Chemistry. a·Jack SaltielW Atom Yee
Jun 7, 2011·The Journal of Physical Chemistry. a·Noriyuki Minezawa, Mark S Gordon
Jan 28, 2014·The Journal of Physical Chemistry. B·M QuickS A Kovalenko
Nov 5, 2014·The Journal of Physical Chemistry. B·Amanda L HoukChristopher G Elles
Nov 12, 2013·Journal of Chemical Theory and Computation·I N Ioffe, A A Granovsky
Feb 6, 2017·The Journal of Chemical Physics·A L DobryakovS A Kovalenko
Apr 17, 2017·The Journal of Chemical Physics·Marc de WergifosseChristopher G Elles
Oct 7, 2017·Journal of the American Chemical Society·Ilya N IoffeSergey A Kovalenko
Apr 20, 2019·The Journal of Physical Chemistry. B·Olivia A KrohnSergey A Kovalenko

❮ Previous
Next ❯

Citations

Sep 28, 2021·Physical Chemistry Chemical Physics : PCCP·Svetlana M SudarkovaSergey A Kovalenko

❮ Previous
Next ❯

Related Concepts

Trending Feeds

COVID-19

Coronaviruses encompass a large family of viruses that cause the common cold as well as more serious diseases, such as the ongoing outbreak of coronavirus disease 2019 (COVID-19; formally known as 2019-nCoV). Coronaviruses can spread from animals to humans; symptoms include fever, cough, shortness of breath, and breathing difficulties; in more severe cases, infection can lead to death. This feed covers recent research on COVID-19.

Blastomycosis

Blastomycosis fungal infections spread through inhaling Blastomyces dermatitidis spores. Discover the latest research on blastomycosis fungal infections here.

Nuclear Pore Complex in ALS/FTD

Alterations in nucleocytoplasmic transport, controlled by the nuclear pore complex, may be involved in the pathomechanism underlying multiple neurodegenerative diseases including Amyotrophic Lateral Sclerosis and Frontotemporal Dementia. Here is the latest research on the nuclear pore complex in ALS and FTD.

Applications of Molecular Barcoding

The concept of molecular barcoding is that each original DNA or RNA molecule is attached to a unique sequence barcode. Sequence reads having different barcodes represent different original molecules, while sequence reads having the same barcode are results of PCR duplication from one original molecule. Discover the latest research on molecular barcoding here.

Chronic Fatigue Syndrome

Chronic fatigue syndrome is a disease characterized by unexplained disabling fatigue; the pathology of which is incompletely understood. Discover the latest research on chronic fatigue syndrome here.

Evolution of Pluripotency

Pluripotency refers to the ability of a cell to develop into three primary germ cell layers of the embryo. This feed focuses on the mechanisms that underlie the evolution of pluripotency. Here is the latest research.

Position Effect Variegation

Position Effect Variagation occurs when a gene is inactivated due to its positioning near heterochromatic regions within a chromosome. Discover the latest research on Position Effect Variagation here.

STING Receptor Agonists

Stimulator of IFN genes (STING) are a group of transmembrane proteins that are involved in the induction of type I interferon that is important in the innate immune response. The stimulation of STING has been an active area of research in the treatment of cancer and infectious diseases. Here is the latest research on STING receptor agonists.

Microbicide

Microbicides are products that can be applied to vaginal or rectal mucosal surfaces with the goal of preventing, or at least significantly reducing, the transmission of sexually transmitted infections. Here is the latest research on microbicides.