Time-resolved spectroscopy
In physics and physical chemistry, time-resolved spectroscopy is the study of dynamic processes in materials or chemical compounds by means of spectroscopic techniques. Most often, processes are studied after the illumination of a material occurs, but in principle, the technique can be applied to any process that leads to a change in properties of a material. With the help of pulsed lasers, it is possible to study processes that occur on time scales as short as 10−16 seconds.
Transient-absorption spectroscopy
Transient-absorption spectroscopy, also known as flash photolysis, is an extension of absorption spectroscopy. Ultrafast transient absorption spectroscopy, an example of non-linear spectroscopy, measures changes in the absorbance/transmittance in the sample. Here, the absorbance at a particular wavelength or range of wavelengths of a sample is measured as a function of time after excitation by a flash of light. In a typical experiment, both the light for excitation and the light for measuring the absorbance are generated by a pulsed laser. If the process under study is slow, then the time resolution can be obtained with a continuous probe beam and repeated conventional spectrophotometric techniques.Time-resolved absorption spectroscopy relies on our ability to resolve two physical actions in real time. The shorter the detection time, the better the resolution. This leads to the idea that femtosecond laser based spectroscopy offers better resolution than nano-second laser based spectroscopy.
In a typical experimental set up, a pump pulse excites the sample and later, a delayed probe pulse strikes the sample. In order to maintain the maximum spectral distribution, two pulses are derived from the same source. The impact of the probe pulse on the sample is recorded and analyzed with wavelength/ time to study the dynamics of the excited state.
Absorbance -Absorbance = Δ Absorbance
Δ Absorbance records any change in the absorption spectrum as a function of time and wavelength. As a matter of fact, it reflects ground state bleaching, further excitation of the excited electrons to higher excited states, stimulated emission or product absorption. Bleaching of ground state refers to depletion of the ground state carriers to excited states. Stimulated emission follows the fluorescence spectrum of the molecule and is Stokes shifted relative to and often still overlaps with the bleach signal. This is a lasing effect of the excited dye molecules under the strong probe light. This emission signal cannot be distinguished from the absorption signal and often gives false negative Δ absorbance peaks in the final spectra that can be decoupled via approximations. Product absorption refers to any absorption changes caused due to formation of intermediate reaction products. TA measurements can also be used to predict non emissive states and dark states unlike time resolved photoluminescence.
Transient absorption can be measured as a function of wavelength or time.
The TA curve along wavelength provides information regarding evolution/decay of various intermediate species involved in chemical reaction at different wavelengths.
The transient absorption decay curve against time contains information regarding the number of decay processes involved at a given wavelength, how fast or slow the decay processes are. It can provide evidences with respect to inter-system crossing, intermediate unstable electronic states, trap states, surface states etc.
Conditions
TA measurements are highly sensitive to laser repetition rate, pulse duration, emission wavelength, polarization, intensity, sample chemistry, solvents, concentration and temperature. The excitation density must be kept low otherwise sample annihilation, saturation and orientational saturation may come into play.Application
Transient absorption spectroscopy helps study the mechanistic and kinetic details of chemical processes occurring on the time scales of few picoseconds to femto-seconds. These chemical events are initiated by an ultrafast laser pulse and are further probed by a probe pulse.With the help of TA measurements, one can look into non-radiative relaxation of higher electronic states, vibrational relaxations and radiative relaxation of excited singlet state.
Transient absorption spectroscopy can be used to trace the intermediate states in a photo-chemical reaction; energy, charge or electron transfer process; conformational changes, thermal relaxation, fluorescence or phosphorescence processes, optical gain spectroscopy of semiconductor laser materials. etc. With the availability of UV-Vis-NIR ultrafast lasers, one can selectively excite a portion of any large molecule to desired excited states to study the specific molecular dynamics.
Transient absorption spectroscopy has become an important tool for characterizing various electronic states and energy transfer processes in nanoparticles, to locate trap states and further helps in characterizing the efficient passivation strategies.
Other multiple-pulse techniques
Transient spectroscopy as discussed above is a technique that involves two pulses. There are many more techniques that employ two or more pulses, such as:- Photon echoes.
- Four-wave mixing
Nuclear magnetic resonance and electron spin resonance are often implemented with multiple-pulse techniques, though with radio waves and micro waves instead of visible light.
Time-resolved infrared spectroscopy
Time-resolved infrared spectroscopy also employs a two-pulse, "pump-probe" methodology. The pump pulse is typically in the UV region and is often generated by a high-powered Nd:YAG laser, whereas the probe beam is in the infrared region. This technique currently operates down to the picosecond time regime and surpasses transient absorption and emission spectroscopy by providing structural information on the excited-state kinetics of both dark and emissive states.Time-resolved fluorescence spectroscopy
Time-resolved fluorescence spectroscopy is an extension of fluorescence spectroscopy. Here, the fluorescence of a sample is monitored as a function of time after excitation by a flash of light. The time resolution can be obtained in a number of ways, depending on the required sensitivity and time resolution:- With fast-detection electronics
- With Time Correlated Single Photon Counting, TCSPC
- With a streak camera
- With intensified CCD cameras
- With optical gating - a short laser pulse acts as a gate for the detection of fluorescence light; only fluorescence light that arrives at the detector at the same time as the gate pulse is detected. This technique has the best time resolution, but the efficiency is rather low. An extension of this optical gating technique is to use a "Kerr gate", which allows the scattered Raman signal to be collected before the fluorescence signal overwhelms it. This technique can greatly improve the signal:noise ratio of Raman spectra.