Vibrational quenching of excitonic splittings in H-bonded molecular dimers: the electronic Davydov splittings cannot match experiment

The Journal of Chemical Physics
Philipp OttigerHorst Köppel

Abstract

The S(1)/S(2) state exciton splittings of symmetric doubly hydrogen-bonded gas-phase dimers provide spectroscopic benchmarks for the excited-state electronic couplings between UV chromophores. These have important implications for electronic energy transfer in multichromophoric systems ranging from photosynthetic light-harvesting antennae to photosynthetic reaction centers, conjugated polymers, molecular crystals, and nucleic acids. We provide laser spectroscopic data on the S(1)/S(2) excitonic splitting Δ(exp) of the doubly H-bonded o-cyanophenol (oCP) dimer and compare to the splittings of the dimers of (2-aminopyridine)(2), [(2AP)(2)], (2-pyridone)(2), [(2PY)(2)], (benzoic acid)(2), [(BZA)(2)], and (benzonitrile)(2), [(BN)(2)]. The experimental S(1)/S(2) excitonic splittings are Δ(exp) = 16.4 cm(-1) for (oCP)(2), 11.5 cm(-1) for (2AP)(2), 43.5 cm(-1) for (2PY)(2), and <1 cm(-1) for (BZA)(2). In contrast, the vertical S(1)/S(2) energy gaps Δ(calc) calculated by the approximate second-order coupled cluster (CC2) method for the same dimers are 10-40 times larger than the Δ(exp) values. The qualitative failure of this and other ab initio methods to reproduce the exciton splitting Δ(exp) arises from the Born-Oppenheimer (BO) appr...Continue Reading

References

Dec 20, 2000·Proceedings of the National Academy of Sciences of the United States of America·J M Jean, K B Hall
Dec 8, 2005·Journal of the American Chemical Society·Dimitra MarkovitsiElodie Lazzarotto
Apr 8, 2006·Annual Review of Physical Chemistry·Frank C Spano
Sep 27, 2006·The Journal of Chemical Physics·Jann A FreySamuel Leutwyler
Mar 31, 2007·Physical Chemistry Chemical Physics : PCCP·Hans-Hermann RitzeDana Nachtigallová
Jul 10, 2008·Physical Chemistry Chemical Physics : PCCP·Arnim HellwegChristof Hättig
Jul 30, 2008·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Ivo KalkmanW Leo Meerts
Oct 29, 2008·Physical Chemistry Chemical Physics : PCCP·Dana NachtigallováHans-Hermann Ritze
Nov 13, 2008·Annual Review of Physical Chemistry·Yuan-Chung Cheng, Graham R Fleming
Nov 18, 2008·Annual Review of Physical Chemistry·Chris T MiddletonBern Kohler
Dec 3, 2008·The Journal of Chemical Physics·Nathan R PillsburyTimothy S Zwier
Apr 1, 2009·The Journal of Physical Chemistry. B·David BeljonneRobert J Silbey
Apr 11, 2009·The Journal of Physical Chemistry. a·Philipp OttigerSamuel Leutwyler
Nov 27, 2009·The Journal of Physical Chemistry. a·Goutham KodaliRobert J Stanley
Jun 10, 2010·The Journal of Physical Chemistry. a·Espen Sagvolden, Filipp Furche
Jun 10, 2010·Physical Chemistry Chemical Physics : PCCP·Vladimir I Novoderezhkin, Rienk van Grondelle
May 3, 2011·The Journal of Chemical Physics·Chirantha P RodrigoTimothy S Zwier
Jun 18, 2011·Chimia·Philipp Ottiger, Samuel Leutwyler
Sep 24, 2011·Nature Chemistry·Gregory D ScholesRienk van Grondelle
Apr 14, 2009·Journal of Chemical Theory and Computation·Espen SagvoldenAndreas Köhn

❮ Previous
Next ❯

Citations

Mar 21, 2013·The Journal of Physical Chemistry. a·Katharina RöttgerFriedrich Temps
Jun 5, 2013·Physical Chemistry Chemical Physics : PCCP·M A Suhm, F Kollipost
Dec 20, 2013·Journal of the Royal Society, Interface·Francesca FassioliGregory D Scholes
Mar 25, 2014·The Journal of Chemical Physics·Gregory D Scholes, Cathal Smyth
Nov 12, 2013·The Journal of Chemical Physics·Pablo García-FernándezAndreas Dreuw
Dec 5, 2012·The Journal of Chemical Physics·Philipp Ottiger, Samuel Leutwyler
Jan 20, 2016·The Journal of Physical Chemistry. B·Jacob C DeanGregory D Scholes
Jan 17, 2016·The Journal of Chemical Physics·Sabine Kopec, Horst Köppel
Mar 18, 2016·Chemical Reviews·Maurizio Becucci, Sonia Melandri
Jan 13, 2015·Annual Review of Physical Chemistry·Andriy Zhugayevych, Sergei Tretiak
Dec 22, 2016·The Journal of Physical Chemistry. a·Franziska A BalmerSamuel Leutwyler
Apr 27, 2018·Physical Chemistry Chemical Physics : PCCP·Aude BouchetAnne Zehnacker
Aug 22, 2017·Physical Chemistry Chemical Physics : PCCP·Mitsuhiko Miyazaki, Masaaki Fujii
Dec 4, 2012·Chemphyschem : a European Journal of Chemical Physics and Physical Chemistry·Yoshiya InokuchiThomas R Rizzo
Sep 1, 2019·The Journal of Chemical Physics·Nathanael M KidwellTimothy S Zwier
Apr 30, 2017·Angewandte Chemie·Ricardo A Mata, Martin A Suhm
Nov 13, 2015·Chemical Science·Philipp OttigerSamuel Leutwyler
Dec 18, 2013·Chemistry : a European Journal·Johannes AhrensMartin Bröring
Mar 27, 2013·The Journal of Physical Chemistry. B·Carolin König, Johannes Neugebauer
Oct 30, 2014·The Journal of Physical Chemistry. a·Franziska A BalmerSamuel Leutwyler
Aug 1, 2014·Journal of the American Chemical Society·Alice CoraniVilly Sundström
Jun 28, 2019·The Journal of Physical Chemistry. a·Sugata GoswamiHorst Köppel
Nov 28, 2017·The Journal of Physical Chemistry. a·Yu XieZhenggang Lan
Feb 9, 2013·The Journal of Physical Chemistry. B·Kurt A KistlerSpiridoula Matsika
Jul 7, 2018·The Journal of Physical Chemistry Letters·Tia S LeeGregory D Scholes

❮ Previous
Next ❯

Methods Mentioned

BETA
chemical treatments

Software Mentioned

vspace
TURBOMOLE

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.