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
Jul 30, 2004·The Journal of Chemical Physics·Petra ImhofKarl Kleinermanns
Nov 13, 2004·Chemical Reviews·Jean-Luc BrédasJérôme Cornil
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
Dec 17, 2008·The Journal of Chemical Physics·Jaime A StearnsDavid F Plusquellic
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
Oct 29, 2009·Journal of the American Chemical Society·Hong-Mei ZhaoBernd Engels
Nov 27, 2009·The Journal of Physical Chemistry. a·Goutham KodaliRobert J Stanley
Dec 2, 2009·The Journal of Chemical Physics·Philipp OttigerHorst Köppel
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 7, 2011·The Journal of Physical Chemistry. a·Shin Grace ChouDavid F Plusquellic
Jun 18, 2011·Chimia·Philipp Ottiger, Samuel Leutwyler
Sep 24, 2011·Nature Chemistry·Gregory D ScholesRienk van Grondelle
Oct 28, 2011·The Journal of Chemical Physics·Cornelia G HeidSamuel Leutwyler
Apr 14, 2009·Journal of Chemical Theory and Computation·Espen SagvoldenAndreas Köhn
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
Nov 21, 2012·The Journal of Chemical Physics·Sabine KopecHorst Köppel
Mar 25, 2014·The Journal of Chemical Physics·Gregory D Scholes, Cathal Smyth
Jun 8, 2013·The Journal of Chemical Physics·Evan G BuchananTimothy S Zwier
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
Mar 3, 2015·The Journal of Chemical Physics·Sabine KopecHorst Köppel
Dec 22, 2016·The Journal of Physical Chemistry. a·Franziska A BalmerSamuel Leutwyler
Jan 19, 2017·The Journal of Physical Chemistry. a·Yoshiya InokuchiTakayuki Ebata
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
May 10, 2013·The Journal of Physical Chemistry. a·M Schröter, O Kühn
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
Sep 5, 2018·Journal of Chemical Theory and Computation·Qinghui Ge, Martin Head-Gordon