Stokes shift is the difference (in energy, wavenumber or frequency units) between positions of the band maxima of the absorption and emission spectra (fluorescence and Raman being two examples) of the same electronic transition. [1] It is named after Irish physicist George Gabriel Stokes. [2] [3] [4]
When a system (be it a molecule or atom) absorbs a photon, it gains energy and enters an excited state. The system can relax by emitting a photon. The Stokes shift occurs when the energy of the emitted photon is lower than that of the absorbed photon, representing the difference in energy of the two photons.
The Stokes shift is primarily the result of two phenomena: vibrational relaxation or dissipation and solvent reorganization. A fluorophore is a part of a molecule with a dipole moment that exhibits fluorescence. When a fluorophore enters an excited state, its dipole moment changes, but surrounding solvent molecules cannot adjust so quickly. Only after vibrational relaxation do their dipole moments realign. [5]
Stokes shifts are given in wavelength units, but this is less meaningful than energy, wavenumber or frequency units because it depends on the absorption wavelength. For instance, a 50 nm Stokes shift from absorption at 300 nm is larger in terms of energy than a 50 nm Stokes shift from absorption at 600 nm.
Stokes fluorescence is the emission of a longer-wavelength photon (lower frequency or energy) by a molecule that has absorbed a photon of shorter wavelength (higher frequency or energy). [6] [7] [8] Both absorption and radiation (emission) of energy are distinctive for a particular molecular structure. If a material has a direct bandgap in the range of visible light, the light shining on it is absorbed, which excites electrons to a higher-energy state. The electrons remain in the excited state for about 10−8 seconds. This number varies over several orders of magnitude, depending on the sample, and is known as the fluorescence lifetime of the sample. After losing a small amount of energy through vibrational relaxation, the molecule returns to the ground state, and energy is emitted.
If the emitted photon has more energy than the absorbed photon, the energy difference is called an anti-Stokes shift; [9] this extra energy comes from dissipation of thermal phonons in a crystal lattice, cooling the crystal in the process. Anti-Stokes shifts may also be due to triplet-triplet annihilation processes, resulting in the formation of higher singlet states that emit at higher energies.
In Raman spectroscopy, when a molecule is excited by incident radiation, it undergoes a Stokes shift as it emits radiation at a lower energy level than the incident radiation. Analyzing the intensity and frequency of the spectral shift provides valuable information about the vibrational modes of molecules, enabling the identification of chemical bonds, functional groups, and molecular conformations.
Yttrium oxysulfide (Y2O2S) doped with gadolinium oxysulfide (Gd2O2S) is a common industrial anti-Stokes pigment, absorbing in the near-infrared and emitting in the visible region of the spectrum. [10] This composite material is often utilized in luminescent applications, where it absorbs lower-energy photons and emits higher-energy photons. This unique property makes it particularly valuable in various technological fields, including security printing, anti-counterfeiting measures, and luminescent displays. By harnessing anti-Stokes fluorescence, this pigment enables the creation of vibrant and durable inks, coatings, and materials with enhanced visibility and authentication capabilities.
Photon upconversion is an anti-Stokes process where lower-energy photons are converted into higher-energy photons. An example of this later process is demonstrated by upconverting nanoparticles. It is more commonly observed in Raman spectroscopy, where it can be used to determine the temperature of a material. [11]
In direct-bandgap thin-film semiconducting layers Stokes shifted emission can originate from three main sources: doping, strain, and disorder. [12] Each of these factors can introduce variations in the energy levels of the semiconductor material, leading to a shift in the emitted light towards longer wavelengths compared to the incident light. This phenomenon is particularly relevant in optoelectronic devices where controlling these factors can be crucial for optimizing device performance.
Fluorescence is one of two kinds of emission of light by a substance that has absorbed light or other electromagnetic radiation. Fluorescence involves no change in electron spin multiplicity and generally it immediately follows absorption; phosphorescence involves spin change and is delayed. Thus fluorescent materials generally cease to glow nearly immediately when the radiation source stops, while phosphorescent materials continue to emit light for some time after.
Spectroscopy is the field of study that measures and interprets electromagnetic spectra. In narrower contexts, spectroscopy is the precise study of color as generalized from visible light to all bands of the electromagnetic spectrum.
Raman spectroscopy is a spectroscopic technique typically used to determine vibrational modes of molecules, although rotational and other low-frequency modes of systems may also be observed. Raman spectroscopy is commonly used in chemistry to provide a structural fingerprint by which molecules can be identified.
A spectral line is a weaker or stronger region in an otherwise uniform and continuous spectrum. It may result from emission or absorption of light in a narrow frequency range, compared with the nearby frequencies. Spectral lines are often used to identify atoms and molecules. These "fingerprints" can be compared to the previously collected ones of atoms and molecules, and are thus used to identify the atomic and molecular components of stars and planets, which would otherwise be impossible.
The emission spectrum of a chemical element or chemical compound is the spectrum of frequencies of electromagnetic radiation emitted due to electrons making a transition from a high energy state to a lower energy state. The photon energy of the emitted photons is equal to the energy difference between the two states. There are many possible electron transitions for each atom, and each transition has a specific energy difference. This collection of different transitions, leading to different radiated wavelengths, make up an emission spectrum. Each element's emission spectrum is unique. Therefore, spectroscopy can be used to identify elements in matter of unknown composition. Similarly, the emission spectra of molecules can be used in chemical analysis of substances.
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.
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.
A fluorophore is a fluorescent chemical compound that can re-emit light upon light excitation. Fluorophores typically contain several combined aromatic groups, or planar or cyclic molecules with several π bonds.
In physics, Raman scattering or the Raman effect is the inelastic scattering of photons by matter, meaning that there is both an exchange of energy and a change in the light's direction. Typically this effect involves vibrational energy being gained by a molecule as incident photons from a visible laser are shifted to lower energy. This is called normal Stokes-Raman scattering.
Resonance Raman spectroscopy is a variant of Raman spectroscopy in which the incident photon energy is close in energy to an electronic transition of a compound or material under examination. This similarity in energy (resonance) leads to greatly increased intensity of the Raman scattering of certain vibrational modes, compared to ordinary Raman spectroscopy.
In quantum mechanics, an absorption band is a range of wavelengths, frequencies or energies in the electromagnetic spectrum that are characteristic of a particular transition from initial to final state in a substance.
Coherent anti-Stokes Raman spectroscopy, also called Coherent anti-Stokes Raman scattering spectroscopy (CARS), is a form of spectroscopy used primarily in chemistry, physics and related fields. It is sensitive to the same vibrational signatures of molecules as seen in Raman spectroscopy, typically the nuclear vibrations of chemical bonds. Unlike Raman spectroscopy, CARS employs multiple photons to address the molecular vibrations, and produces a coherent signal. As a result, CARS is orders of magnitude stronger than spontaneous Raman emission. CARS is a third-order nonlinear optical process involving three laser beams: a pump beam of frequency ωp, a Stokes beam of frequency ωS and a probe beam at frequency ωpr. These beams interact with the sample and generate a coherent optical signal at the anti-Stokes frequency (ωpr+ωp-ωS). The latter is resonantly enhanced when the frequency difference between the pump and the Stokes beams (ωp-ωS) coincides with the frequency of a Raman resonance, which is the basis of the technique's intrinsic vibrational contrast mechanism.
Ultrafast laser spectroscopy is a category of spectroscopic techniques using 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.
Chemical imaging is the analytical capability to create a visual image of components distribution from simultaneous measurement of spectra and spatial, time information. Hyperspectral imaging measures contiguous spectral bands, as opposed to multispectral imaging which measures spaced spectral bands.
Fluorescence is used in the life sciences generally as a non-destructive way of tracking or analysing biological molecules. Some proteins or small molecules in cells are naturally fluorescent, which is called intrinsic fluorescence or autofluorescence. Alternatively, specific or general proteins, nucleic acids, lipids or small molecules can be "labelled" with an extrinsic fluorophore, a fluorescent dye which can be a small molecule, protein or quantum dot. Several techniques exist to exploit additional properties of fluorophores, such as fluorescence resonance energy transfer, where the energy is passed non-radiatively to a particular neighbouring dye, allowing proximity or protein activation to be detected; another is the change in properties, such as intensity, of certain dyes depending on their environment allowing their use in structural studies.
Photoluminescence excitation is a specific type of photoluminescence and concerns the interaction between electromagnetic radiation and matter. It is used in spectroscopic measurements where the frequency of the excitation light is varied, and the luminescence is monitored at the typical emission frequency of the material being studied. Peaks in the PLE spectra often represent absorption lines of the material. PLE spectroscopy is a useful method to investigate the electronic level structure of materials with low absorption due to the superior signal-to-noise ratio of the method compared to absorption measurements.
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.
A luminescent solar concentrator (LSC) is a device for concentrating radiation, solar radiation in particular, to produce electricity. Luminescent solar concentrators operate on the principle of collecting radiation over a large area, converting it by luminescence and directing the generated radiation into relatively small photovoltaic solar cells at the edges.
Photon upconversion (UC) is a process in which the sequential absorption of two or more photons leads to the emission of light at shorter wavelength than the excitation wavelength. It is an anti-Stokes type emission. An example is the conversion of infrared light to visible light. Upconversion can take place in both organic and inorganic materials, through a number of different mechanisms. Organic molecules that can achieve photon upconversion through triplet-triplet annihilation are typically polycyclic aromatic hydrocarbons (PAHs). Inorganic materials capable of photon upconversion often contain ions of d-block or f-block elements. Examples of these ions are Ln3+, Ti2+, Ni2+, Mo3+, Re4+, Os4+, and so on.
Stimulated Raman spectroscopy, also referred to as stimulated Raman scattering (SRS), is a form of spectroscopy employed in physics, chemistry, biology, and other fields. The basic mechanism resembles that of spontaneous Raman spectroscopy: a pump photon, of the angular frequency , which is scattered by a molecule has some small probability of inducing some vibrational transition, as opposed to inducing a simple Rayleigh transition. This makes the molecule emit a photon at a shifted frequency. However, SRS, as opposed to spontaneous Raman spectroscopy, is a third-order non-linear phenomenon involving a second photon—the Stokes photon of angular frequency —which stimulates a specific transition. When the difference in frequency between both photons resembles that of a specific vibrational transition the occurrence of this transition is resonantly enhanced. In SRS, the signal is equivalent to changes in the intensity of the pump and Stokes beams. The signals are typically rather low, of the order of a part in 10^5, thus calling for modulation-transfer techniques: one beam is modulated in amplitude, and the signal is detected on the other beam via a lock-in amplifier. Employing a pump laser beam of a constant frequency and a Stokes laser beam of a scanned frequency allows for unraveling the molecule's spectral fingerprint. This spectral fingerprint differs from those obtained by other spectroscopy methods, such as Rayleigh scattering, as the Raman transitions confer different exclusion rules than those that apply to Rayleigh transitions.