Fluctuations and single molecules

The fluorescence of single molecules coupled to a thermal bath is studied both experimentally and theoretically. The effect of different fluctuations on the coherence properties of resonance fluorescence is considered first. Coherence is measured in an interference experiment where a single molecule is used as a light source. A standard approach based on the optical Bloch equations apparently provides quite an accurate description of the interference experiment. Systems with long correlation times (where spectra are time dependent on any timescale) are considered next. It is shown that intensity-time-frequency correlation spectroscopy, which provides both high signal-to-noise ratio and high time resolution, is very suitable for such a case. The Bloch equations are further tested in an experiment where the shape of an excitation spectral line of a single molecule is accurately measured over six orders of magnitude of the exciting laser power. Significant deviations from the predictions of the Bloch equations are found. The role of critical parameters-the correlation time of the bath, the Rabi oscillation period, and the coupling constant between the bath and the molecule-is discussed. The paper also includes a short general introduction to the methodology of single-molecule studies.

Optical Bloch equations and enhanced decay of Rabi oscillations in strong driving fields

Optical Bloch equations are widely used for describing dynamics in a system consisting molecules, electromagnetic waves, and a thermal bath. We analyze applicability of these equations to a single molecule imbedded in a solid matrix. Classical Bloch equations and the limits of their applicability are derived from more general master equations. Simple and intuitively appealing picture based on stochastic Bloch equations shows that at low temperatures, contrary to common believes, a strong driving field can not only suppress but can also increase decay rates of Rabi oscillations. A physical system where predicted effects can be observed experimentally is suggested. (c) 2005 Elsevier B.V. All rights reserved.

Bath house, Cleveland Point House, Cleveland

New bath house under construction (centre), with existing buildings to either side.

Bath house, Cleveland Point House, Cleveland

Bath house under construction, as seen looking towards water from deck area.

Bath house, Cleveland Point House, Cleveland

As seen looking towards water from deck area.

Bath house hip rafters, Cleveland Point House, Cleveland

Timber framing to new bath house.

Bath house section, Cleveland Point House, Cleveland

Section taken through new bath house.

Bath house, Cleveland Point House, Cleveland

Timber framing to new bath house, as seen from beachfront.

Bath house, Cleveland Point House, Cleveland

Timber framing to new bath house, as seen looking towards water from deck area (to be constructed).

Bath house, Cleveland Point House, Cleveland

As seen looking towards water from deck area.

Bath house, Cleveland Point House, Cleveland

New bath house (centre), with existing buildings to either side.

Thermal Cycling Stability of Silica Membranes for Gas Separation

Hydrogen is being seen as an alternative energy carrier to conventional hydrocarbons to reduce greenhouse gas emissions. High efficiency separation technologies to remove hydrogen from the greenhouse gas, carbon dioxide, are therefore in growing demand. Traditional thermodynamic separation systems utilise distillation, absorption and adsorption, but are limited in efficiency at compact scales. Molecular sieve silica (MSS) membranes can perform this separation as they have high permselectivity of hydrogen to carbon dioxide, but their stability under thermal cycling is not well reported. In this work we exposed a standard MSS membrane and a carbonised template MSS (CTMSS) membrane to thermal cycling from 100 to 450°C. The standard MSS and carbonised template CTMSS membranes both showed permselectivity of helium to nitrogen dropping from around 10 to 6 in the first set of cycles, remaining stable until the last test. The permselectivity drop was due to small micropore collapse, which occurred via structure movement during cycling. Simulating single stage membrane separation with a 50:50 molar feed of H2:CO2, H2 exiting the permeate stream would start at 79% and stabilise at 67%. Higher selectivity membranes showed less of a purity drop, indicating the margin at which to design a stable membrane separation unit for CO2 capture.

Bath house pavilion, Lake Weyba House, Sunshine Coast

South-West elevation. Paved seating area in foreground.

Bath house pavilion, Lake Weyba House, Sunshine Coast

Link to bedroom pavilion on right; roof of main pavilion on left.