Calculations of nonlinear wave-packet interferometry signals in the pump-probe limit as tests for vibrational control over electronic excitation transfer

Jason D Biggs, Jeffrey A Cina
Journal of Chemical Physics 2009 December 14, 131 (22): 224302
The preceding paper [J. D. Biggs and J. A. Cina, J. Chem. Phys. 131, 224101 (2009)] (referred to here as Paper 1), describes a strategy for externally influencing the course of short-time electronic excitation transfer (EET) in molecular dimers and observing the process by nonlinear wave-packet interferometry (nl-WPI). External influence can, for example, be exerted by inducing coherent intramolecular vibration in one of the chromophores prior to short-pulse electronic excitation of the other. Within a sample of isotropically oriented dimers having a specified internal geometry, a vibrational mode internal to the acceptor chromophore can be preferentially driven by electronically nonresonant impulsive stimulated Raman (or resonant infrared) excitation with a short polarized "control" pulse. A subsequent electronically resonant polarized pump then preferentially excites the donor, and EET ensues. Paper 1 investigates control-pulse-influenced nl-WPI as a tool for the spectroscopic evaluation of the effect of coherent molecular vibration on excitation transfer, presenting general expressions for the nl-WPI difference signal from a dimer following the action of a control pulse of arbitrary polarization and shape. Electronic excitation is to be effected and its interchromophore transfer monitored by resonant pump and probe "pulses," respectively, each consisting of an optical-phase-controlled ultrashort pulse-pair having arbitrary polarization, duration, center frequency, and other characteristics. Here we test both the control strategy and its spectroscopic investigation-with some sacrifice of amplitude-level detail-by calculating the pump-probe difference signal. That signal is the limiting case of the control-influenced nl-WPI signal in which the two pulses in the pump pulse-pair coincide, as do the two pulses in the probe pulse-pair. We present calculated pump-probe difference signals for (1) a model excitation-transfer complex in which two equal-energy monomers each support one moderately Franck-Condon active intramolecular vibration; (2) a simplified model of the covalent dimer dithia-anthracenophane, representing its EET dynamics following selective impulsive excitation of the weakly Franck-Condon active nu(12) anthracene vibration at 385 cm(-1); and (3) a model complex featuring moderate electronic-vibrational coupling in which the site energy of the acceptor chromophore is lower than that of the donor.

Full Text Links

Find Full Text Links for this Article


You are not logged in. Sign Up or Log In to join the discussion.

Related Papers

Remove bar
Read by QxMD icon Read

Save your favorite articles in one place with a free QxMD account.


Search Tips

Use Boolean operators: AND/OR

diabetic AND foot
diabetes OR diabetic

Exclude a word using the 'minus' sign

Virchow -triad

Use Parentheses

water AND (cup OR glass)

Add an asterisk (*) at end of a word to include word stems

Neuro* will search for Neurology, Neuroscientist, Neurological, and so on

Use quotes to search for an exact phrase

"primary prevention of cancer"
(heart or cardiac or cardio*) AND arrest -"American Heart Association"