Rotational Temperature
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Rotational Temperature
The characteristic rotational temperature ( or ) is commonly used in statistical thermodynamics to simplify the expression of the rotational partition function and the rotational contribution to molecular thermodynamic properties. It has units of temperature and is defined asP. Atkins and J. de Paula "Physical Chemistry", 9th edition (W.H. Freeman 2010), p.597 :\theta_ = \frac = \frac, where \overline = B/hc is the rotational constant, is a molecular moment of inertia, is the Planck constant, is the speed of light, is the reduced Planck constant and is the Boltzmann constant. The physical meaning of is as an estimate of the temperature at which thermal energy (of the order of ) is comparable to the spacing between rotational energy levels (of the order of ). At about this temperature the population of excited rotational levels becomes important. Some typical values are given in the table. In each case the value refers to the most common isotopic species. References See al ...
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Statistical Thermodynamics
In physics, statistical mechanics is a mathematical framework that applies Statistics, statistical methods and probability theory to large assemblies of microscopic entities. It does not assume or postulate any natural laws, but explains the macroscopic behavior of nature from the behavior of such ensembles. Statistical mechanics arose out of the development of classical thermodynamics, a field for which it was successful in explaining macroscopic physical properties—such as temperature, pressure, and heat capacity—in terms of microscopic parameters that fluctuate about average values and are characterized by probability distributions. This established the fields of statistical thermodynamics and statistical physics. The founding of the field of statistical mechanics is generally credited to three physicists: *Ludwig Boltzmann, who developed the fundamental interpretation of entropy in terms of a collection of microstates *James Clerk Maxwell, who developed models of probab ...
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Rotational Partition Function
In chemistry, the rotational partition function relates the rotational degrees of freedom to the rotational part of the energy. Definition The total canonical partition function Z of a system of N identical, indistinguishable, noninteracting atoms or molecules can be divided into the atomic or molecular partition functions \zeta: Z = \frac with: \zeta = \sum_j g_j e^ , where g_j is the degeneracy of the ''j''-th quantum level of an individual particle, k_\text is the Boltzmann constant, and T is the absolute temperature of system. For molecules, under the assumption that total energy levels E_j can be partitioned into its contributions from different degrees of freedom (weakly coupled degrees of freedom) E_j = \sum_i E_j^i = E_j^\text + E_j^\text + E_j^\text + E_j^\text + E_j^\text and the number of degenerate states are given as products of the single contributions g_j = \prod_i g_j^i = g_j^\text g_j^\text g_j^\text g_j^\text g_j^\text, where "trans", "ns", "rot", "vib ...
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Temperature
Temperature is a physical quantity that expresses quantitatively the perceptions of hotness and coldness. Temperature is measured with a thermometer. Thermometers are calibrated in various temperature scales that historically have relied on various reference points and thermometric substances for definition. The most common scales are the Celsius scale with the unit symbol °C (formerly called ''centigrade''), the Fahrenheit scale (°F), and the Kelvin scale (K), the latter being used predominantly for scientific purposes. The kelvin is one of the seven base units in the International System of Units (SI). Absolute zero, i.e., zero kelvin or −273.15 °C, is the lowest point in the thermodynamic temperature scale. Experimentally, it can be approached very closely but not actually reached, as recognized in the third law of thermodynamics. It would be impossible to extract energy as heat from a body at that temperature. Temperature is important in all fields of natur ...
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Rigid Rotor
In rotordynamics, the rigid rotor is a mechanical model of rotating systems. An arbitrary rigid rotor is a 3-dimensional rigid object, such as a top. To orient such an object in space requires three angles, known as Euler angles. A special rigid rotor is the ''linear rotor'' requiring only two angles to describe, for example of a diatomic molecule. More general molecules are 3-dimensional, such as water (asymmetric rotor), ammonia (symmetric rotor), or methane (spherical rotor). Linear rotor The linear rigid rotor model consists of two point masses located at fixed distances from their center of mass. The fixed distance between the two masses and the values of the masses are the only characteristics of the rigid model. However, for many actual diatomics this model is too restrictive since distances are usually not completely fixed. Corrections on the rigid model can be made to compensate for small variations in the distance. Even in such a case the rigid rotor model is a u ...
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Moment Of Inertia
The moment of inertia, otherwise known as the mass moment of inertia, angular mass, second moment of mass, or most accurately, rotational inertia, of a rigid body is a quantity that determines the torque needed for a desired angular acceleration about a rotational axis, akin to how mass determines the force needed for a desired acceleration. It depends on the body's mass distribution and the axis chosen, with larger moments requiring more torque to change the body's rate of rotation. It is an extensive (additive) property: for a point mass the moment of inertia is simply the mass times the square of the perpendicular distance to the axis of rotation. The moment of inertia of a rigid composite system is the sum of the moments of inertia of its component subsystems (all taken about the same axis). Its simplest definition is the second moment of mass with respect to distance from an axis. For bodies constrained to rotate in a plane, only their moment of inertia about an axis ...
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Planck Constant
The Planck constant, or Planck's constant, is a fundamental physical constant of foundational importance in quantum mechanics. The constant gives the relationship between the energy of a photon and its frequency, and by the mass-energy equivalence, the relationship between mass and frequency. Specifically, a photon's energy is equal to its frequency multiplied by the Planck constant. The constant is generally denoted by h. The reduced Planck constant, or Dirac constant, equal to the constant divided by 2 \pi, is denoted by \hbar. In metrology it is used, together with other constants, to define the kilogram, the SI unit of mass. The SI units are defined in such a way that, when the Planck constant is expressed in SI units, it has the exact value The constant was first postulated by Max Planck in 1900 as part of a solution to the ultraviolet catastrophe. At the end of the 19th century, accurate measurements of the spectrum of black body radiation existed, but the distribut ...
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Speed Of Light
The speed of light in vacuum, commonly denoted , is a universal physical constant that is important in many areas of physics. The speed of light is exactly equal to ). According to the special theory of relativity, is the upper limit for the speed at which conventional matter or energy (and thus any signal carrying information) can travel through space. All forms of electromagnetic radiation, including visible light, travel at the speed of light. For many practical purposes, light and other electromagnetic waves will appear to propagate instantaneously, but for long distances and very sensitive measurements, their finite speed has noticeable effects. Starlight viewed on Earth left the stars many years ago, allowing humans to study the history of the universe by viewing distant objects. When communicating with distant space probes, it can take minutes to hours for signals to travel from Earth to the spacecraft and vice versa. In computing, the speed of light fixes ...
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Reduced Planck Constant
The Planck constant, or Planck's constant, is a fundamental physical constant of foundational importance in quantum mechanics. The constant gives the relationship between the energy of a photon and its frequency, and by the mass-energy equivalence, the relationship between mass and frequency. Specifically, a photon's energy is equal to its frequency multiplied by the Planck constant. The constant is generally denoted by h. The reduced Planck constant, or Dirac constant, equal to the constant divided by 2 \pi, is denoted by \hbar. In metrology it is used, together with other constants, to define the kilogram, the SI unit of mass. The SI units are defined in such a way that, when the Planck constant is expressed in SI units, it has the exact value The constant was first postulated by Max Planck in 1900 as part of a solution to the ultraviolet catastrophe. At the end of the 19th century, accurate measurements of the spectrum of black body radiation existed, but the distribut ...
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Boltzmann Constant
The Boltzmann constant ( or ) is the proportionality factor that relates the average relative kinetic energy of particles in a gas with the thermodynamic temperature of the gas. It occurs in the definitions of the kelvin and the gas constant, and in Planck's law of black-body radiation and Boltzmann's entropy formula, and is used in calculating thermal noise in resistors. The Boltzmann constant has dimensions of energy divided by temperature, the same as entropy. It is named after the Austrian scientist Ludwig Boltzmann. As part of the 2019 redefinition of SI base units, the Boltzmann constant is one of the seven " defining constants" that have been given exact definitions. They are used in various combinations to define the seven SI base units. The Boltzmann constant is defined to be exactly . Roles of the Boltzmann constant Macroscopically, the ideal gas law states that, for an ideal gas, the product of pressure and volume is proportional to the product of amount of ...
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Thermal Energy
The term "thermal energy" is used loosely in various contexts in physics and engineering. It can refer to several different well-defined physical concepts. These include the internal energy or enthalpy of a body of matter and radiation; heat, defined as a type of energy transfer (as is thermodynamic work); and the characteristic energy of a degree of freedom, k_T, in a system that is described in terms of its microscopic particulate constituents (where T denotes temperature and k_ denotes the Boltzmann constant). Relation to heat and internal energy In thermodynamics, heat is energy transferred to or from a thermodynamic system by mechanisms other than thermodynamic work or transfer of matter, such as conduction, radiation, and friction. Heat refers to a quantity transferred between systems, not to a property of any one system, or "contained" within it. On the other hand, internal energy and enthalpy are properties of a single system. Heat and work depend on the way in which ...
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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 ene ...
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Vibrational Temperature
The vibrational temperature is commonly used in thermodynamics, to simplify certain equations. It has units of temperature and is defined as \theta _= \frac = \frac where k_B is Boltzmann's constant, c is the speed of light, and \nu (Greek letter nu) is the characteristic frequency of the oscillator. The vibrational temperature is used commonly when finding the vibrational partition function. ReferencesStatistical thermodynamics University Arizona


See also

*Rotational temperature *Rotational spectroscopy *Vibrational spectroscopy *Infrared spectroscopy *Spectroscopy Atomic physics Molecular physics {{thermodynamics-stub ...
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