The vibrational temperature is commonly used in thermodynamics, to simplify certain equations. It has units of temperature and is defined as
where is the Boltzmann constant, is the speed of light, and (Greek letter nu) is the characteristic frequency of the oscillator.
The vibrational temperature is used commonly when finding the vibrational partition function.
| Molecule | ||
|---|---|---|
| N2 | 2446 cm−1 | 3521 K |
| O2 | 1568 cm−1 | 2256 K |
| F2 | 917 cm−1 | 1320 K |
| HF | 4138 cm−1 | 5957 K |
| HCl | 2991 cm−1 | 4303 K |
In thermodynamics, the specific heat capacity of a substance is the amount of heat that must be added to one unit of mass of the substance in order to cause an increase of one unit in temperature. It is also referred to as massic heat capacity or as the specific heat. More formally it is the heat capacity of a sample of the substance divided by the mass of the sample. The SI unit of specific heat capacity is joule per kelvin per kilogram, J⋅kg−1⋅K−1. For example, the heat required to raise the temperature of 1 kg of water by 1 K is 4184 joules, so the specific heat capacity of water is 4184 J⋅kg−1⋅K−1.
In fluid mechanics, the Grashof number is a dimensionless number which approximates the ratio of the buoyancy to viscous forces acting on a fluid. It frequently arises in the study of situations involving natural convection and is analogous to the Reynolds number.
A quantum mechanical system or particle that is bound—that is, confined spatially—can only take on certain discrete values of energy, called energy levels. This contrasts with classical particles, which can have any amount of energy. The term is commonly used for the energy levels of the electrons in atoms, ions, or molecules, which are bound by the electric field of the nucleus, but can also refer to energy levels of nuclei or vibrational or rotational energy levels in molecules. The energy spectrum of a system with such discrete energy levels is said to be quantized.
An ideal gas is a theoretical gas composed of many randomly moving point particles that are not subject to interparticle interactions. The ideal gas concept is useful because it obeys the ideal gas law, a simplified equation of state, and is amenable to analysis under statistical mechanics. The requirement of zero interaction can often be relaxed if, for example, the interaction is perfectly elastic or regarded as point-like collisions.
In thermodynamics, the Joule–Thomson effect describes the temperature change of a real gas or liquid when it is forced through a valve or porous plug while keeping it insulated so that no heat is exchanged with the environment. This procedure is called a throttling process or Joule–Thomson process. At room temperature, all gases except hydrogen, helium, and neon cool upon expansion by the Joule–Thomson process when being throttled through an orifice; these three gases experience the same effect but only at lower temperatures. Most liquids such as hydraulic oils will be warmed by the Joule–Thomson throttling process.
In physics, the Rayleigh–Jeans law is an approximation to the spectral radiance of electromagnetic radiation as a function of wavelength from a black body at a given temperature through classical arguments. For wavelength λ, it is
In physics, black hole thermodynamics is the area of study that seeks to reconcile the laws of thermodynamics with the existence of black hole event horizons. As the study of the statistical mechanics of black-body radiation led to the development of the theory of quantum mechanics, the effort to understand the statistical mechanics of black holes has had a deep impact upon the understanding of quantum gravity, leading to the formulation of the holographic principle.
Certain systems can achieve negative thermodynamic temperature; that is, their temperature can be expressed as a negative quantity on the Kelvin or Rankine scales. This should be distinguished from temperatures expressed as negative numbers on non-thermodynamic Celsius or Fahrenheit scales, which are nevertheless higher than absolute zero. A system with a truly negative temperature on the Kelvin scale is hotter than any system with a positive temperature. If a negative-temperature system and a positive-temperature system come in contact, heat will flow from the negative- to the positive-temperature system. A standard example of such a system is population inversion in laser physics.
In thermodynamics and solid-state physics, the Debye model is a method developed by Peter Debye in 1912 to estimate phonon contribution to the specific heat in a solid. It treats the vibrations of the atomic lattice (heat) as phonons in a box in contrast to the Einstein photoelectron model, which treats the solid as many individual, non-interacting quantum harmonic oscillators. The Debye model correctly predicts the low-temperature dependence of the heat capacity of solids, which is proportional to – the Debye T 3 law. Similarly to the Einstein photoelectron model, it recovers the Dulong–Petit law at high temperatures. Due to simplifying assumptions, its accuracy suffers at intermediate temperatures.
Rotational–vibrational spectroscopy is a branch of molecular spectroscopy that is concerned with infrared and Raman spectra of molecules in the gas phase. Transitions involving changes in both vibrational and rotational states can be abbreviated as rovibrational transitions. When such transitions emit or absorb photons, the frequency is proportional to the difference in energy levels and can be detected by certain kinds of spectroscopy. Since changes in rotational energy levels are typically much smaller than changes in vibrational energy levels, changes in rotational state are said to give fine structure to the vibrational spectrum. For a given vibrational transition, the same theoretical treatment as for pure rotational spectroscopy gives the rotational quantum numbers, energy levels, and selection rules. In linear and spherical top molecules, rotational lines are found as simple progressions at both higher and lower frequencies relative to the pure vibration frequency. In symmetric top molecules the transitions are classified as parallel when the dipole moment change is parallel to the principal axis of rotation, and perpendicular when the change is perpendicular to that axis. The ro-vibrational spectrum of the asymmetric rotor water is important because of the presence of water vapor in the atmosphere.
In classical statistical mechanics, the equipartition theorem relates the temperature of a system to its average energies. The equipartition theorem is also known as the law of equipartition, equipartition of energy, or simply equipartition. The original idea of equipartition was that, in thermal equilibrium, energy is shared equally among all of its various forms; for example, the average kinetic energy per degree of freedom in translational motion of a molecule should equal that in rotational motion.
Rotational spectroscopy is concerned with the measurement of the energies of transitions between quantized rotational states of molecules in the gas phase. The rotational spectrum 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 where rotational, vibrational and electronic energy changes occur simultaneously.
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.
The vibrational partition function traditionally refers to the component of the canonical partition function resulting from the vibrational degrees of freedom of a system. The vibrational partition function is only well-defined in model systems where the vibrational motion is relatively uncoupled with the system's other degrees of freedom.
The characteristic rotational temperature 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 as
The concept entropy was first developed by German physicist Rudolf Clausius in the mid-nineteenth century as a thermodynamic property that predicts that certain spontaneous processes are irreversible or impossible. In statistical mechanics, entropy is formulated as a statistical property using probability theory. The statistical entropy perspective was introduced in 1870 by Austrian physicist Ludwig Boltzmann, who established a new field of physics that provided the descriptive linkage between the macroscopic observation of nature and the microscopic view based on the rigorous treatment of large ensembles of microscopic states that constitute thermodynamic systems.
A molecular vibration is a periodic motion of the atoms of a molecule relative to each other, such that the center of mass of the molecule remains unchanged. The typical vibrational frequencies range from less than 1013 Hz to approximately 1014 Hz, corresponding to wavenumbers of approximately 300 to 3000 cm−1 and wavelengths of approximately 30 to 3 µm.
In physics and chemistry, a degree of freedom is an independent physical parameter in the formal description of the state of a physical system. The set of all states of a system is known as the system's phase space, and the degrees of freedom of the system are the dimensions of the phase space.
In chemistry, the rotational partition function relates the rotational degrees of freedom to the rotational part of the energy.
In chemistry, NMR line broadening techniques can be used to determine the rate constant and the Gibbs free energy of exchange reactions of two different chemical compounds. If the two species are in equilibrium and exchange to each other, peaks of both species get broadened in the spectrum. This observation of broadened peaks can be used to obtain kinetic and thermodynamic information of the exchange reaction.
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