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Two-photon Circular Dichroism
Two-photon circular dichroism (TPCD), the nonlinear counterpart of electronic circular dichroism (ECD), is defined as the differences between the two-photon absorption (TPA) cross-sections obtained using left circular polarized light and right circular polarized light (see Figure 1). Background Typically, two-photon absorption (TPA) takes place at twice the wavelength as one-photon absorption (OPA). This feature allows for the TPCD based study of chiral systems in the far to near ultraviolet (UV) region. ECD cannot be employed in this region due to interferences from strong linear absorption of typical buffers and solvents and also because of the scattering exhibited by inhomogeneous samples in this region. Several other advantages are associated with the use of non-linear absorption, i.e. high spatial resolution, enhanced penetration depth, improved background discrimination and reduced photodamage to living specimens. In addition, the fact that TPA transitions obey differe ...
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Comparative Schematic Between One And Two Photon Processes
general linguistics, the comparative is a syntactic construction that serves to express a comparison between two (or more) entities or groups of entities in quality or degree - see also comparison (grammar) for an overview of comparison, as well as positive and superlative degrees of comparison. The syntax of comparative constructions is poorly understood due to the complexity of the data. In particular, the comparative frequently occurs with independent mechanisms of syntax such as coordination and forms of ellipsis ( gapping, pseudogapping, null complement anaphora, stripping, verb phrase ellipsis). The interaction of the various mechanisms complicates the analysis. Absolute and null forms A number of fixed expressions use a comparative form where no comparison is being asserted, such as ''higher education'' or ''younger generation''. These comparatives can be called ''absolute''. Similarly, a null comparative is one in which the starting point for comparison is not stat ...
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Chirality (chemistry)
In chemistry, a molecule or ion is called chiral () if it cannot be superposed on its mirror image by any combination of rotations, translations, and some conformational changes. This geometric property is called chirality (). The terms are derived from Ancient Greek χείρ (''cheir'') 'hand'; which is the canonical example of an object with this property. A chiral molecule or ion exists in two stereoisomers that are mirror images of each other, called enantiomers; they are often distinguished as either "right-handed" or "left-handed" by their absolute configuration or some other criterion. The two enantiomers have the same chemical properties, except when reacting with other chiral compounds. They also have the same physical properties, except that they often have opposite optical activities. A homogeneous mixture of the two enantiomers in equal parts is said to be racemic, and it usually differs chemically and physically from the pure enantiomers. Chiral molecule ...
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Specific Rotation
In chemistry, specific rotation ( �'') is a property of a chiral chemical compound. It is defined as the change in orientation of monochromatic plane-polarized light, per unit distance–concentration product, as the light passes through a sample of a compound in solution. Compounds which rotate the plane of polarization of a beam of plane polarized light clockwise are said to be dextrorotary, and correspond with positive specific rotation values, while compounds which rotate the plane of polarization of plane polarized light counterclockwise are said to be levorotary, and correspond with negative values. If a compound is able to rotate the plane of polarization of plane-polarized light, it is said to be “ optically active”. Specific rotation is an intensive property, distinguishing it from the more general phenomenon of optical rotation. As such, the ''observed'' rotation (α) of a sample of a compound can be used to quantify the enantiomeric excess of that compound ...
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Raman Optical Activity
Raman optical activity (ROA) is a vibrational spectroscopic technique that is reliant on the difference in intensity of Raman scattered right and left circularly polarised light due to molecular chirality. History of Raman optical activity The field began with the doctoral work of Laurence D. Barron with Peter Atkins at the University of Oxford and was later further developed by Barron with David Buckingham at the University of Cambridge. More developments, including important contributions to the development of practical Raman optical activity instruments, were made by Werner Hug of the University of Fribourg, and Lutz Hecht with Laurence Barron at the University of Glasgow. Theory of Raman optical activity The basic principle of Raman optical activity is that there is interference between light waves scattered by the polarizability and optical activity tensors of a chiral molecule, which leads to a difference between the intensities of the right- and left-handed cir ...
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Polarization Rotator
A polarization rotator is an optical device that rotates the polarization axis of a linearly polarized light beam by an angle of choice. Such devices can be based on the Faraday effect, on birefringence, or on total internal reflection.F. J. Duarte''Tunable Laser Optics'', 2nd Edition (CRC, New York, 2015) Chapter 5 Rotators of linearly polarized light have found widespread applications in modern optics since laser beams tend to be linearly polarized and it is often necessary to rotate the original polarization to its orthogonal alternative. Faraday rotators A Faraday rotator consists of an optical material in a magnetic field. When light propagates in the material, interaction with the magnetic field causes left- and right-handed circularly polarized waves to propagate with slightly different phase velocities. Since a linearly-polarized wave can be described as a superposition of left- and right-handed circularly polarized waves, the difference in phase velocity causes th ...
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Polarization (waves)
Polarization ( also polarisation) is a property applying to transverse waves that specifies the geometrical orientation of the oscillations. In a transverse wave, the direction of the oscillation is perpendicular to the direction of motion of the wave. A simple example of a polarized transverse wave is vibrations traveling along a taut string ''(see image)''; for example, in a musical instrument like a guitar string. Depending on how the string is plucked, the vibrations can be in a vertical direction, horizontal direction, or at any angle perpendicular to the string. In contrast, in longitudinal waves, such as sound waves in a liquid or gas, the displacement of the particles in the oscillation is always in the direction of propagation, so these waves do not exhibit polarization. Transverse waves that exhibit polarization include electromagnetic waves such as light and radio waves, gravitational waves, and transverse sound waves ( shear waves) in solids. An electromagneti ...
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Levorotation And Dextrorotation
Optical rotation, also known as polarization rotation or circular birefringence, is the rotation of the orientation of the plane of polarization about the optical axis of linearly polarized light as it travels through certain materials. Circular birefringence and circular dichroism are the manifestations of optical activity. Optical activity occurs only in chiral materials, those lacking microscopic mirror symmetry. Unlike other sources of birefringence which alter a beam's state of polarization, optical activity can be observed in fluids. This can include gases or solutions of chiral molecules such as sugars, molecules with helical secondary structure such as some proteins, and also chiral liquid crystals. It can also be observed in chiral solids such as certain crystals with a rotation between adjacent crystal planes (such as quartz) or metamaterials. When looking at the source of light, the rotation of the plane of polarization may be either to the right (dextrorotatory or ...
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Geometric Phase
In classical and quantum mechanics, geometric phase is a phase difference acquired over the course of a cycle, when a system is subjected to cyclic adiabatic processes, which results from the geometrical properties of the parameter space of the Hamiltonian. The phenomenon was independently discovered by S. Pancharatnam (1956), in classical optics and by H. C. Longuet-Higgins (1958)See page 12 in molecular physics; it was generalized by Sir Michael Berry in (1984). It is also known as the Pancharatnam–Berry phase, Pancharatnam phase, or Berry phase. It can be seen in the conical intersection of potential energy surfaces and in the Aharonov–Bohm effect. Geometric phase around the conical intersection involving the ground electronic state of the C6H3F3+ molecular ion is discussed on pages 385–386 of the textbook by Bunker and Jensen. In the case of the Aharonov–Bohm effect, the adiabatic parameter is the magnetic field enclosed by two interference paths, and it ...
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Cryptochirality
In stereochemistry, cryptochirality is a special case of chirality in which a molecule is chiral but its specific rotation is non-measurable. The underlying reason for the lack of rotation is the specific electronic properties of the molecule. The term was introduced by Kurt Mislow in 1977. For example, the alkane 5-ethyl-5-propylundecane found in certain species of ''Phaseolus vulgaris'' is chiral at its central quaternary carbon, but neither enantiomeric form has any observable optical rotation: It is still possible to distinguish between the two enantiomers by using them in asymmetric synthesis of another chemical whose stereochemical nature can be measured. For example, the Soai reaction of 2-(3,3-dimethylbut-1-ynyl)pyrimidine-5-carbaldehyde with diisopropylzinc performed in the presence of 5-ethyl-5-propylundecane forms a secondary alcohol with a high enantiomeric excess In stereochemistry, enantiomeric excess (ee) is a measurement of purity used for chiral substances. ...
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Birefringence
Birefringence is the optical property of a material having a refractive index that depends on the polarization and propagation direction of light. These optically anisotropic materials are said to be birefringent (or birefractive). The birefringence is often quantified as the maximum difference between refractive indices exhibited by the material. Crystals with non-cubic crystal structures are often birefringent, as are plastics under mechanical stress. Birefringence is responsible for the phenomenon of double refraction whereby a ray of light, when incident upon a birefringent material, is split by polarization into two rays taking slightly different paths. This effect was first described by Danish scientist Rasmus Bartholin in 1669, who observed it in calcite, a crystal having one of the strongest birefringences. In the 19th century Augustin-Jean Fresnel described the phenomenon in terms of polarization, understanding light as a wave with field components in transverse pola ...
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