2. ultrafast absorption-difference at 5 K monshouwer, baltuska, van mourik & van grondelle, j. phys. chem. a 1998 photosynthetic electronic energy transfer can be accompanied by vibrational coherence transfer LH1-RC structure cogdell et al. science 2003 fluorescence up- conversion at room temperature bradforth, jimenez, van mourik, van grondell & fleming, j. phys. chem. 1995

3. vibrational coherence transfer and trapping … energy transfer complexes cina & fleming j phys chem a 2004 state-1 (eg) state-1’ (ge)

4. state-1’ (ge) state-1 (eg) franck-condon-excited wave packet wave-packet trajectory in donor- excited state affects short-time EET biggs & cina jcp submitted 2009

5. state-1’ (ge) state-1 (eg) franck-condon-excited wave packet initially-displaced wave packet wave-packet trajectory in donor- excited state affects short-time EET biggs & cina jcp submitted 2009

6. wave-packet trajectory in donor- excited state affects short-time EET biggs & cina jcp submitted 2009 state-1’ (ge) state-1 (eg) franck-condon-excited wave packet initially-displaced wave packet P eg (t)  1’ 11 donor-state population oriented model system horizontally polarized pump without or with prior displacement to q b = - d

7. vibrationally-perturbed nl-WPI (& pump-probe spectroscopy) on a collection of identical, randomly oriented dimers both monomers unexcited —> “acceptor” excited —><— both monomers excited <— “donor” excited signal is the population of one-exciton manifold 2 nd -order in sub-resonant “control” pulse and quadrilinear in the wpi-pulses having a given optical phase-signature all pulses nonzero duration, independently polarized pulse sequence:

8. in the pump-probe limit of nl-WPI difference measurement, pulse sequence simplifies …

10. for example, nl-WPI signal contribution with phase-signature iswith pump-probe limit:

12. for example, nl-WPI signal contribution with phase-signature iswith

14. the corresponding nuclear wave packet is a linear superposition of the form

15. electronic state- space pathways contributing to

16. initial trajectories in donor-excited state state-1’ (ge) state-1 (eg) franck-condon- excited wave packet initially-displaced wave packet

17. initial trajectories in donor-excited state state-1’ (ge) state-1 (eg) franck-condon- excited wave packet initially-displaced wave packet generated by ISRS & short- pulse electronic absorption ISRS generates nuclear motion with maximum displacement less than d

18. donor-excited state population donor-state population of oriented model system after interaction with vertically polarized ISRS & horizontally polarized pump pulses  1’ 11 franck-condon-excited wave packet ISRS-generated wave packet

19. pump-probe & pump-probe difference signals from isotropic sample without & with stimulated-Raman excitation P-pulse ISRS polarization pump (A) & probe (C) polarization

20. P-pulse ISRS polarization pump (A) & probe (C) polarization (simulated-emission contribution to) pump-probe & pump-probe difference signals from an oriented sample  1’ 11

21. pump-probe & pump-probe difference signals from isotropic, inhomogeneously broadened sample site energies chosen from independent Gaussian distributions of FWHM  pulse parameters same as before, except

22. accelerated EET in the downhill case? initially-displaced wave packet franck-condon- excited wave packet

23. donor-excited state population in downhill EET donor-state population of oriented downhill system after interaction with vertically polarized ISRS & horizontally polarized pump pulses  1’ 11 ISRS-generated wave packet franck-condon-excited wave packet

24. pump-probe & pump-probe difference signals from isotropic sample of downhill EET complex P-pulse ISRS polarization pump (A) & probe (C) polarization VHH HH

25. pump-probe difference signal pump-probe signal VHH HH contributions to signals from downhill EET complex: stimulated-emission excited-state absorption ground-state bleach

26. ISRS (P) & probe (C) polarization pump (A) polarization pump-probe & pump-probe difference signals from isotropic sample of downhill EET complex V-polarized & red-shifted probe VHV HVHV

27. dithia-anthracenophane (DTA) anthracene monomer fluorescence lambert et al. JCP 1984 DTA fluorescence anisotropy yamazaki et al. j phys chem A 2002   = 385 cm -1   = 0.557 J = 22.9 cm -1   = 1400 cm -1   = 1.05

28. pulse power spectra & schematic absorption spectra P-pulse (ISRS) anthracene anthracene-12 A-pulse (pump) C-pulse (probe)

29. (t - t A )/  12 donor-state population with ISRS without ISRS DTA-12 donor-state population dynamics

30. polarized pump-probe & pump-probe difference signals from DTA-12 pump-probe pump-probe difference VHH HH anisotropy stimulated-emission only other parameters the same, except 100-cm -1 site-energy broadening

31. q b /d when, the survival probability reduces to idiosyncracies of (antisymmetric-mode) Franck-Condon overlaps may offer a prospect for exerting vibrational control over EET, even in the weak electronic-vibrational coupling case. in DTA-12, for example, q a /d donor-state population

32. next steps … vibrational control of EET in (biological?) multi-chromophore complexes optimize duration, center frequency, and chirp-rate of P-pulse for large-amplitude acceptor-mode displacement calculate & interpret full nl-WPI difference signals, with all polarization combinations include vibrational relaxation and dephasing via Redfield theory calculate & interpret nl-WPI difference signals from Jahn-Teller active (or other) systems with conical intersections following ISRS-excitation of coherent pseudo-rotation; prepare & observe dynamical Slonczewski resonances? vibrational control of EET in (biological?) multi-chromophore complexes optimize duration, center frequency, and chirp-rate of P-pulse for large-amplitude acceptor-mode displacement calculate & interpret full nl-WPI difference signals, with all polarization combinations include vibrational relaxation and dephasing via Redfield theory calculate & interpret nl-WPI difference signals from Jahn-Teller active (or other) systems with conical intersections following ISRS-excitation of coherent pseudo-rotation; prepare & observe dynamical Slonczewski resonances?