Long-lived oscillations in 2D spectra of chlorophylls are at the heart of an ongoing debate. Their physical origin is either a multipigment effect, such as excitonic coherence, or localized vibrations. We show how relative phase differences of diagonal- and cross-peak oscillations can distinguish between electronic and vibrational (vibronic) effects. While direct discrimination between the two scenarios is obscured when peaks overlap, their sensitivity to temperature provides a stronger argument. We show that vibrational (vibronic) oscillations change relative phase with temperature, while electronic oscillations are only weakly dependent. This highlights that studies of relative phase difference as a function of temperature provide a clear and easily accessible method to distinguish between vibrational and electronic coherences.
References
J Phys Chem Lett. 2012 Jun 7;3(11):1497-502
[PMID: 26285628]
J Phys Chem A. 2008 May 8;112(18):4254-60
[PMID: 18376878]
Proc Natl Acad Sci U S A. 2011 Dec 27;108(52):20908-12
[PMID: 22167798]
J Phys Chem B. 2013 Aug 15;117(32):9380-5
[PMID: 23879880]
Proc Natl Acad Sci U S A. 2010 Jul 20;107(29):12766-70
[PMID: 20615985]
Proc Natl Acad Sci U S A. 2013 Jan 22;110(4):1203-8
[PMID: 23267114]
J Chem Phys. 2012 Jun 21;136(23):234501
[PMID: 22779600]
J Phys Chem B. 2011 May 12;115(18):5383-91
[PMID: 21329370]
Annu Rev Phys Chem. 2003;54:425-63
[PMID: 12626736]
J Phys Chem A. 2013 Jul 25;117(29):6007-14
[PMID: 23461650]