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. All time-resolved spectra are suitable to be analyzed using the two-dimensional correlation method for a correlation map between the peaks.
Transient-absorption spectroscopy (TAS), 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 ('pump') and the light for measuring the absorbance ('probe') are generated by a pulsed laser. If the process under study is slow, then the time resolution can be obtained with a continuous (i.e., not pulsed) 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 (after pump) – Absorbance (before pump) = ΔAbsorbance
ΔAbsorbance records any change in the absorption spectrum as a function of time and wavelength. As a matter of fact, it reflects ground state bleaching (-ΔA), further excitation of the excited electrons to higher excited states(+ΔA), stimulated emission(-ΔA) or product absorption(+ΔA). 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 (coherent emission) 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.
Transient absorption is a highly sensitive technique that can provide insightful information regarding chemical and material processes when achieving sufficient spectral resolution. Beyond the obvious consideration of a sufficiently short pulse width, the dependence of the frequency bandwidth must be accounted for. The equation
Informs us that, for any beam shape (K), the beam bandwidth (Δν) is inversely proportional to its pulse width. Therefore, a compromise must be made to achieve maximum resolution in both the time and frequency domains.
The use of high-power lasers with ultrashort pulse widths can create phenomena that obscure weak spectral data, commonly referred to as artifacts. Examples of artifacts include the signal resulting from two-photon absorption and stimulated Raman amplification. Two-photon absorption occurs in samples that are generally transparent to UV-Vis wavelengths of light. These media are able to absorb light efficiently when simultaneously interacting with multiple photons. This causes a change in intensity of the probe pulse.
The above equation describes the change in intensity relative to the number of photons absorbed (γ) and the thickness of the sample (L). The change in absorption signal resulting from this event has been approximated to the below equation.
A common baseline correction technique used in spectroscopy is the penalized root mean square error. A variant of this technique, the asymmetric penalized root mean square, has been used to correct signals affected by artifacts in transient absorption.
TA measurements are highly sensitive to laser repetition rate, pulse duration, emission wavelength, polarization, intensity, sample chemistry, solvents, concentration and temperature. The excitation density (no. of photons per unit area per second) must be kept low otherwise sample annihilation, saturation and orientational saturation may come into play.
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 (~femtoseconds), vibrational relaxations (~picoseconds) and radiative relaxation of excited singlet state (occurs typically on nanoseconds time scale).
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.
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:
The interpretation of experimental data from these techniques is usually much more complicated than in transient-absorption spectroscopy.
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 (TRIR) 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 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:
This technique uses convolution integral to calculate a lifetime from a fluorescence decay.
Time-resolved photoemission spectroscopyand two-photon photoelectron spectroscopy (2PPE) are important extensions to photoemission spectroscopy. These methods employ a pump-probe setup. In most cases the pump and probe are both generated by a pulsed laser and in the UV region. The pump excites the atom or molecule of interest, and the probe ionizes it. The electrons or positive ions resulting from this event are then detected. As the time delay between the pump and the probe are changed, the change in the energy (and sometimes emission direction) of the photo-products is observed. In some cases multiple photons of a lower energy are used as the ionizing probe.
Infrared spectroscopy is the measurement of the interaction of infrared radiation with matter by absorption, emission, or reflection. It is used to study and identify chemical substances or functional groups in solid, liquid, or gaseous forms. It can be used to characterize new materials or identify and verify known and unknown samples. The method or technique of infrared spectroscopy is conducted with an instrument called an infrared spectrometer which produces an infrared spectrum. An IR spectrum can be visualized in a graph of infrared light absorbance on the vertical axis vs. frequency, wavenumber or wavelength on the horizontal axis. Typical units of wavenumber used in IR spectra are reciprocal centimeters, with the symbol cm−1. Units of IR wavelength are commonly given in micrometers, symbol μm, which are related to the wavenumber in a reciprocal way. A common laboratory instrument that uses this technique is a Fourier transform infrared (FTIR) spectrometer. Two-dimensional IR is also possible as discussed below.
Photoluminescence is light emission from any form of matter after the absorption of photons. It is one of many forms of luminescence and is initiated by photoexcitation, hence the prefix photo-. Following excitation, various relaxation processes typically occur in which other photons are re-radiated. Time periods between absorption and emission may vary: ranging from short femtosecond-regime for emission involving free-carrier plasma in inorganic semiconductors up to milliseconds for phosphoresence processes in molecular systems; and under special circumstances delay of emission may even span to minutes or hours.
Mode locking is a technique in optics by which a laser can be made to produce pulses of light of extremely short duration, on the order of picoseconds (10−12 s) or femtoseconds (10−15 s). A laser operated in this way is sometimes referred to as a femtosecond laser, for example, in modern refractive surgery. The basis of the technique is to induce a fixed phase relationship between the longitudinal modes of the laser's resonant cavity. Constructive interference between these modes can cause the laser light to be produced as a train of pulses. The laser is then said to be "phase-locked" or "mode-locked".
Fluorescence spectroscopy is a type of electromagnetic spectroscopy that analyzes fluorescence from a sample. It involves using a beam of light, usually ultraviolet light, that excites the electrons in molecules of certain compounds and causes them to emit light; typically, but not necessarily, visible light. A complementary technique is absorption spectroscopy. In the special case of single molecule fluorescence spectroscopy, intensity fluctuations from the emitted light are measured from either single fluorophores, or pairs of fluorophores.
Photoemission electron microscopy is a type of electron microscopy that utilizes local variations in electron emission to generate image contrast. The excitation is usually produced by ultraviolet light, synchrotron radiation or X-ray sources. PEEM measures the coefficient indirectly by collecting the emitted secondary electrons generated in the electron cascade that follows the creation of the primary core hole in the absorption process. PEEM is a surface sensitive technique because the emitted electrons originate from a shallow layer. In physics, this technique is referred to as PEEM, which goes together naturally with low-energy electron diffraction (LEED), and low-energy electron microscopy (LEEM). In biology, it is called photoelectron microscopy (PEM), which fits with photoelectron spectroscopy (PES), transmission electron microscopy (TEM), and scanning electron microscopy (SEM).
In physics, terahertz time-domain spectroscopy (THz-TDS) is a spectroscopic technique in which the properties of matter are probed with short pulses of terahertz radiation. The generation and detection scheme is sensitive to the sample's effect on both the amplitude and the phase of the terahertz radiation.
Two-photon excitation microscopy is a fluorescence imaging technique that is particularly well-suited to image scattering living tissue of up to about one millimeter in thickness. Unlike traditional fluorescence microscopy, where the excitation wavelength is shorter than the emission wavelength, two-photon excitation requires simultaneous excitation by two photons with longer wavelength than the emitted light. The laser is focused onto a specific location in the tissue and scanned across the sample to sequentially produce the image. Due to the non-linearity of two-photon excitation, mainly fluorophores in the micrometer-sized focus of the laser beam are excited, which results in the spatial resolution of the image. This contrasts with confocal microscopy, where the spatial resolution is produced by the interaction of excitation focus and the confined detection with a pinhole.
Flash photolysis is a pump-probe laboratory technique, in which a sample is first excited by a strong pulse of light from a pulsed laser of nanosecond, picosecond, or femtosecond pulse width or by another short-pulse light source such as a flash lamp. This first strong pulse is called the pump pulse and starts a chemical reaction or leads to an increased population for energy levels other than the ground state within a sample of atoms or molecules. Typically the absorption of light by the sample is recorded within short time intervals to monitor relaxation or reaction processes initiated by the pump pulse.
Ultrafast laser spectroscopy is a spectroscopic technique that uses ultrashort pulse lasers for the study of dynamics on extremely short time scales. Different methods are used to examine the dynamics of charge carriers, atoms, and molecules. Many different procedures have been developed spanning different time scales and photon energy ranges; some common methods are listed below.
In atomic physics, two-photon absorption, also called two-photon excitation or non-linear absorption, is the simultaneous absorption of two photons of identical or different frequencies in order to excite a molecule from one state to a higher energy, most commonly an excited electronic state. Absorption of two photons with different frequencies is called non-degenerate two-photon absorption. Since TPA depends on the simultaneous absorption of two photons, the probability of TPA is proportional to the square of the light intensity; thus it is a nonlinear optical process. The energy difference between the involved lower and upper states of the molecule is equal or smaller than the sum of the photon energies of the two photons absorbed. Two-photon absorption is a third-order process, with absorption cross section typically several orders of magnitude smaller than one-photon absorption cross section.
Photoelectrochemical processes are processes in photoelectrochemistry; they usually involve transforming light into other forms of energy. These processes apply to photochemistry, optically pumped lasers, sensitized solar cells, luminescence, and photochromism.
Terahertz spectroscopy detects and controls properties of matter with electromagnetic fields that are in the frequency range between a few hundred gigahertz and several terahertz. In many-body systems, several of the relevant states have an energy difference that matches with the energy of a THz photon. Therefore, THz spectroscopy provides a particularly powerful method in resolving and controlling individual transitions between different many-body states. By doing this, one gains new insights about many-body quantum kinetics and how that can be utilized in developing new technologies that are optimized up to the elementary quantum level.
Ultrafast electron diffraction (UED), also known as femtosecond electron diffraction (FED), is a pump-probe experimental method based on the combination of optical pump-probe spectroscopy and electron diffraction. UED provides information on the dynamical changes of the structure of materials. It is very similar to time resolved crystallography, but instead of using X-rays as the probe, it uses electrons. In the UED technique, a femtosecond (fs) laser optical pulse excites (pumps) a sample into an excited, usually non-equilibrium, state. The pump pulse may induce chemical, electronic or structural transitions. After a finite time interval, a fs electron pulse is incident upon the sample. The electron pulse undergoes diffraction as a result of interacting with the sample. The diffraction signal is, subsequently, detected by an electron counting instrument such as a CCD camera. Specifically, after the electron pulse diffracts from the sample, the scattered electrons will form a diffraction pattern (image) on a CCD camera. This pattern contains structural information about the sample. By adjusting the time difference between the arrival of the pump and probe beams, one can obtain a series of diffraction patterns as a function of the various time differences. The diffraction data series can be concatenated in order to produce a motion picture of the changes that occurred in the data. UED can provide a wealth of dynamics on charge carriers, atoms, and molecules.
Time-resolved two-photon photoelectron (2PPE) spectroscopy is a time-resolved spectroscopy technique which is used to study electronic structure and electronic excitations at surfaces. The technique utilizes femtosecond to picosecond laser pulses in order to first photoexcite an electron. After a time delay, the excited electron is photoemitted into a free electron state by a second pulse. The kinetic energy and the emission angle of the photoelectron are measured in an electron energy analyzer. To facilitate investigations on the population and relaxation pathways of the excitation, this measurement is performed at different time delays.
Cho Minhaeng is a South Korean scientist in researching physical chemistry, spectroscopy, and microscopy. He was director of the National Creative Research Initiative Center for Coherent Multidimensional Spectroscopy and is founding director of the Center for Molecular Spectroscopy and Dynamics in the Institute for Basic Science (IBS), located in Korea University.
Pump–probe microscopy is a non-linear optical imaging modality used in femtochemistry to study chemical reactions. It generates high-contrast images from endogenous non-fluorescent targets. It has numerous applications, including materials science, medicine, and art restoration.
Fluorescence imaging is a type of non-invasive imaging technique that can help visualize biological processes taking place in a living organism. Images can be produced from a variety of methods including: microscopy, imaging probes, and spectroscopy.
Ultrafast scanning electron microscopy (UFSEM) combines two microscopic modalities, Pump-probe microscopy and Scanning electron microscope, to gather temporal and spatial resolution phenomena. The technique uses ultrashort laser pulses for pump excitation of the material and the sample response will be detected by an Everhart-Thornley detector. Acquiring data depends mainly on formation of images by raster scan mode after pumping with short laser pulse at different delay times. The characterization of the output image will be done through the temporal resolution aspect. Thus, the idea is to exploit the shorter DeBroglie wavelength in respect to the photons which has great impact to increase the resolution about 1 nm. That technique is an up-to-date approach to study the dynamic of charge on material surfaces.
In atomic physics, non-degenerate two-photon absorption or two-color two-photon excitation is a type of two-photon absorption (TPA) where two photons with different energies are (almost) simultaneously absorbed by a molecule, promoting a molecular electronic transition from a lower energy state to a higher energy state. The sum of the energies of the two photons is equal to, or larger than, the total energy of the transition.