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Rotational Correlation Time
Rotational correlation time (\tau_c) is the average time it takes for a molecule to rotate one radian. In solution, rotational correlation times are in the order of picoseconds. For example, the \tau_c = 1.7 ps for water, and 100 ps for a pyrroline nitroxyl radical in a DMSO-water mixture. Rotational correlation times are employed in the measurement of microviscosity (viscosity at the molecular level) and in protein characterization. Rotational correlation times may be measured by rotational (microwave), dielectric, and nuclear magnetic resonance (NMR) spectroscopy. Rotational correlation times of probe molecules in media have been measured by fluorescence lifetime or for radicals, from the linewidths of electron spin resonance Electron paramagnetic resonance (EPR) or electron spin resonance (ESR) spectroscopy is a method for studying materials that have unpaired electrons. The basic concepts of EPR are analogous to those of nuclear magnetic resonance (NMR), but the sp ...s. ...
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Molecule
A molecule is a group of two or more atoms held together by attractive forces known as chemical bonds; depending on context, the term may or may not include ions which satisfy this criterion. In quantum physics, organic chemistry, and biochemistry, the distinction from ions is dropped and ''molecule'' is often used when referring to polyatomic ions. A molecule may be homonuclear, that is, it consists of atoms of one chemical element, e.g. two atoms in the oxygen molecule (O2); or it may be heteronuclear, a chemical compound composed of more than one element, e.g. water (molecule), water (two hydrogen atoms and one oxygen atom; H2O). In the kinetic theory of gases, the term ''molecule'' is often used for any gaseous particle regardless of its composition. This relaxes the requirement that a molecule contains two or more atoms, since the noble gases are individual atoms. Atoms and complexes connected by non-covalent interactions, such as hydrogen bonds or ionic bonds, are typic ...
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Radian
The radian, denoted by the symbol rad, is the unit of angle in the International System of Units (SI) and is the standard unit of angular measure used in many areas of mathematics. The unit was formerly an SI supplementary unit (before that category was abolished in 1995). The radian is defined in the SI as being a dimensionless unit, with 1 rad = 1. Its symbol is accordingly often omitted, especially in mathematical writing. Definition One radian is defined as the angle subtended from the center of a circle which intercepts an arc equal in length to the radius of the circle. More generally, the magnitude in radians of a subtended angle is equal to the ratio of the arc length to the radius of the circle; that is, \theta = \frac, where is the subtended angle in radians, is arc length, and is radius. A right angle is exactly \frac radians. The rotation angle (360°) corresponding to one complete revolution is the length of the circumference divided by the radius, whi ...
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Picosecond
A picosecond (abbreviated as ps) is a unit of time in the International System of Units (SI) equal to 10−12 or (one trillionth) of a second. That is one trillionth, or one millionth of one millionth of a second, or 0.000 000 000 001 seconds. A picosecond is to one second as one second is to approximately 31,689 years. Multiple technical approaches achieve imaging within single-digit picoseconds: for example, the streak camera or intensified CCD (ICCD) cameras are able to picture the motion of light. One picosecond is equal to 1000 femtoseconds, or 1/1000 nanoseconds. Because the next SI unit is 1000 times larger, measurements of 10−11 and 10−10 second are typically expressed as tens or hundreds of picoseconds. Some notable measurements in this range include: * 1.0 picoseconds (1.0 ps) – cycle time for electromagnetic frequency 1 terahertz (THz) (1 x 1012 hertz), an inverse unit. This corresponds to a wavelength of 0.3 mm, as can be calculated by ...
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Microviscosity
Microviscosity, also known as microscopic viscosity, is the friction experienced by a single particle undergoing diffusion because of its interaction with its environment at the micrometer length scale. The concept of microviscosity is intimately related to the concept of single particle diffusion and can be measured using microrheology. Understanding microviscosity requires an understanding of viscosity and diffusion i.e. macroscopic viscosity and bulk diffusion and where their assumptions break down at the micro to nanometer scale where physicists are still trying to replace phenomenological laws with physical laws governing the behavior of single particle mobility. In the field of biophysics, a typical microviscosity problem is understanding how a biomolecule's mobility is hindered within a cellular compartment which will depend upon many factors such as the size, shape, charge, quantity and density of both the diffusing particle and all members of its environment. M ...
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Rotational Spectroscopy
Rotational spectroscopy is concerned with the measurement of the energies of transitions between quantized rotational states of molecules in the gas phase. The spectra of polar molecules can be measured in absorption or emission by microwave spectroscopy or by far infrared spectroscopy. The rotational spectra of non-polar molecules cannot be observed by those methods, but can be observed and measured by Raman spectroscopy. Rotational spectroscopy is sometimes referred to as ''pure'' rotational spectroscopy to distinguish it from rotational-vibrational spectroscopy where changes in rotational energy occur together with changes in vibrational energy, and also from ro-vibronic spectroscopy (or just vibronic spectroscopy) where rotational, vibrational and electronic energy changes occur simultaneously. For rotational spectroscopy, molecules are classified according to symmetry into spherical top, linear and symmetric top; analytical expressions can be derived for the rotational ...
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Dielectric Spectroscopy
Dielectric spectroscopy (which falls in a subcategory of impedance spectroscopy) measures the dielectric properties of a medium as a function of frequency.Kremer F., Schonhals A., Luck W. Broadband Dielectric Spectroscopy. – Springer-Verlag, 2002. It is based on the interaction of an external field with the electric dipole moment of the sample, often expressed by permittivity. It is also an experimental method of characterizing electrochemical systems. This technique measures the impedance of a system over a range of frequencies, and therefore the frequency response of the system, including the energy storage and dissipation properties, is revealed. Often, data obtained by electrochemical impedance spectroscopy (EIS) is expressed graphically in a Bode plot or a Nyquist plot. Impedance is the opposition to the flow of alternating current (AC) in a complex system. A passive complex electrical system comprises both energy dissipater (resistor) and energy storage (capacitor) elem ...
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Nuclear Magnetic Resonance Spectroscopy
Nuclear magnetic resonance spectroscopy, most commonly known as NMR spectroscopy or magnetic resonance spectroscopy (MRS), is a spectroscopic technique to observe local magnetic fields around atomic nuclei. The sample is placed in a magnetic field and the NMR signal is produced by excitation of the nuclei sample with radio waves into nuclear magnetic resonance, which is detected with sensitive radio receivers. The intramolecular magnetic field around an atom in a molecule changes the resonance frequency, thus giving access to details of the electronic structure of a molecule and its individual functional groups. As the fields are unique or highly characteristic to individual compounds, in modern organic chemistry practice, NMR spectroscopy is the definitive method to identify monomolecular organic compounds. The principle of NMR usually involves three sequential steps: # The alignment (polarization) of the magnetic nuclear spins in an applied, constant magnetic field B0. # The ...
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Fluorescence
Fluorescence is the emission of light by a substance that has absorbed light or other electromagnetic radiation. It is a form of luminescence. In most cases, the emitted light has a longer wavelength, and therefore a lower photon energy, than the absorbed radiation. A perceptible example of fluorescence occurs when the absorbed radiation is in the ultraviolet region of the electromagnetic spectrum (invisible to the human eye), while the emitted light is in the visible region; this gives the fluorescent substance a distinct color that can only be seen when the substance has been exposed to UV light. Fluorescent materials cease to glow nearly immediately when the radiation source stops, unlike phosphorescent materials, which continue to emit light for some time after. Fluorescence has many practical applications, including mineralogy, gemology, medicine, chemical sensors (fluorescence spectroscopy), fluorescent labelling, dyes, biological detectors, cosmic-ray detection, vac ...
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Radical (chemistry)
In chemistry, a radical, also known as a free radical, is an atom, molecule, or ion that has at least one unpaired valence electron. With some exceptions, these unpaired electrons make radicals highly chemically reactive. Many radicals spontaneously dimerize. Most organic radicals have short lifetimes. A notable example of a radical is the hydroxyl radical (HO·), a molecule that has one unpaired electron on the oxygen atom. Two other examples are triplet oxygen and triplet carbene (꞉) which have two unpaired electrons. Radicals may be generated in a number of ways, but typical methods involve redox reactions. Ionizing radiation, heat, electrical discharges, and electrolysis are known to produce radicals. Radicals are intermediates in many chemical reactions, more so than is apparent from the balanced equations. Radicals are important in combustion, atmospheric chemistry, polymerization, plasma chemistry, biochemistry, and many other chemical processes. A majority ...
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Electron Spin Resonance
Electron paramagnetic resonance (EPR) or electron spin resonance (ESR) spectroscopy is a method for studying materials that have unpaired electrons. The basic concepts of EPR are analogous to those of nuclear magnetic resonance (NMR), but the spins excited are those of the electrons instead of the atomic nuclei. EPR spectroscopy is particularly useful for studying metal complexes and organic radicals. EPR was first observed in Kazan State University by Soviet physicist Yevgeny Zavoisky in 1944, and was developed independently at the same time by Brebis Bleaney at the University of Oxford. Theory Origin of an EPR signal Every electron has a magnetic moment and spin quantum number s = \tfrac , with magnetic components m_\mathrm = + \tfrac or m_\mathrm = - \tfrac . In the presence of an external magnetic field with strength B_\mathrm , the electron's magnetic moment aligns itself either antiparallel ( m_\mathrm = - \tfrac ) or parallel ( m_\mathrm = + \tfrac ) to the f ...
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Molecular Dynamics
Molecular dynamics (MD) is a computer simulation method for analyzing the physical movements of atoms and molecules. The atoms and molecules are allowed to interact for a fixed period of time, giving a view of the dynamic "evolution" of the system. In the most common version, the trajectories of atoms and molecules are determined by numerically solving Newton's equations of motion for a system of interacting particles, where forces between the particles and their potential energies are often calculated using interatomic potentials or molecular mechanical force fields. The method is applied mostly in chemical physics, materials science, and biophysics. Because molecular systems typically consist of a vast number of particles, it is impossible to determine the properties of such complex systems analytically; MD simulation circumvents this problem by using numerical methods. However, long MD simulations are mathematically ill-conditioned, generating cumulative erro ...
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