Chemistry on Ultrafast and Ultrasmall Scales Trevor Smith Ken Ghiggino Paul Mulvaney School of Chemistry, University of Melbourne
Ultrasmall - techniques l Confocal and multiphoton microscopy l Single molecule detection and emission spectroscopy l FCS, antibunching l Polymers & quantum dots l Total internal reflection fluorescence (EWIF)
Ultrasmall - facilities l Scanning confocal and multiphoton microscopy l Time-resolved fluorescence imaging LaVision PicoStar TCSPC (EI, Becker & Hickl, other) l Single molecule detection and emission spectroscopy l FCS, antibunching, single molecule spectroscopy (spectrograph/CCD) l Polymers & quantum dots l Total internal reflection fluorescence (EWIF) l Scanning near field (SNOM)
Ultrafast - techniques l Time-correlated single photon counting l Time-resolved fluorescence anisotropy l Flash photolysis l Pump-probe techniques l Time-resolved absorption l Fluorescence upconversion l Multi-pulse, multi-wavelength photon echoe
Ultrafast - facilities l Nanosecond flash photolysis (Nd:YAG/OPO) l ns gated CCD/spectrometer l Picosecond dye lasers l Femtosecond Ti:sapphire systems l oscillator/OPO system Pulse picked/cavity dumped MHz rep. rates, nJ pulse energies, tuneable l amplified femtosecond Ti:sapphire oscillator/OPA <280 kHz rep. rates, µJ-10s of nJ pulse energies, tuneable
Facilities l Synthesis l Light emitting polymers (PPVs) l Quantum dots
Evanescent Waves n1n1 n2n2 n1> n2n1> n2 Standing wave Total internal reflection (if i > c ) Evanescent wave E=E o exp(-x/ ) Refraction (if i < c ) Incident Beam, E o Interface Normal ii
l EWIF spectroscopy l EWIF-FCS l Time-resolved EWIFS l Time-resolved EWIF anisotropy l Time-resolved EWIF microscopy
l Expressions for polarisations perpendicular, s, & parallel, p, to plane of incidence: l In bulk solution: l In-plane: l Out-of-plane: Polarised EWIF z x y
TREWIF Anisotropy Time (ns) BULK = 64 nm = 76 nm = 113 nm INCREASING DISTANCE AWAY FROM INTERFACE r(t)
“In-plane” and “Out-of- Plane” anisotropy
Time-resolved EWIF microscopy l Resolution from interface ~10’s of nm