Rotational spectroscopy in the context of "Far infrared"

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⭐ Core Definition: 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 rotational spectrum (power spectral density vs. rotational frequency) 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 tops, linear molecules, and symmetric tops; analytical expressions can be derived for the rotational energy terms of these molecules. Analytical expressions can be derived for the fourth category, asymmetric top, for rotational levels up to J=3, but higher energy levels need to be determined using numerical methods. The rotational energies are derived theoretically by considering the molecules to be rigid rotors and then applying extra terms to account for centrifugal distortion, fine structure, hyperfine structure and Coriolis coupling. Fitting the spectra to the theoretical expressions gives numerical values of the angular moments of inertia from which very precise values of molecular bond lengths and angles can be derived in favorable cases. In the presence of an electrostatic field there is Stark splitting which allows molecular electric dipole moments to be determined.

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Rotational spectroscopy in the context of Rigid body

In physics, a rigid body, also known as a rigid object, is a solid body in which deformation is zero or negligible, when a deforming pressure or deforming force is applied on it. The distance between any two given points on a rigid body remains constant in time regardless of external forces or moments exerted on it. A rigid body is usually considered as a continuous distribution of mass. Mechanics of rigid bodies is a field within mechanics where motions and forces of objects are studied without considering effects that can cause deformation (as opposed to mechanics of materials, where deformable objects are considered).

In the study of special relativity, a perfectly rigid body does not exist; and objects can only be assumed to be rigid if they are not moving near the speed of light, where the mass is infinitely large. In quantum mechanics, a rigid body is usually thought of as a collection of point masses. For instance, molecules (consisting of the point masses: electrons and nuclei) are often seen as rigid bodies (see classification of molecules as rigid rotors).

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Rotational spectroscopy in the context of Infra-red (IR) spectroscopy

Infrared spectroscopy (IR spectroscopy or vibrational spectroscopy) is the measurement of the interaction of infrared radiation with matter by absorption, emission, or reflection. It is used to study and identify chemical substances or functional groups in solid, liquid, or gaseous forms. It can be used to characterize new materials or identify and verify known and unknown samples. The method or technique of infrared spectroscopy is conducted with an instrument called an infrared spectrometer (or spectrophotometer) which produces an infrared spectrum. An IR spectrum can be visualized in a graph of infrared light absorbance (or transmittance) on the vertical axis vs. frequency, wavenumber or wavelength on the horizontal axis. Typical units of wavenumber used in IR spectra are reciprocal centimeters, with the symbol cm. Units of IR wavelength are commonly given in micrometers (formerly called "microns"), symbol μm, which are related to the wavenumber in a reciprocal way. A common laboratory instrument that uses this technique is a Fourier transform infrared (FTIR) spectrometer. Two-dimensional IR is also possible as discussed below.

The infrared portion of the electromagnetic spectrum is usually divided into three regions; the near-, mid- and far- infrared, named for their relation to the visible spectrum. The higher-energy near-IR, approximately 14,000–4,000 cm (0.7–2.5 μm wavelength) can excite overtone or combination modes of molecular vibrations. The mid-infrared, approximately 4,000–400 cm (2.5–25 μm) is generally used to study the fundamental vibrations and associated rotational–vibrational structure. The far-infrared, approximately 400–10 cm (25–1,000 μm) has low energy and may be used for rotational spectroscopy and low frequency vibrations. The region from 2–130 cm, bordering the microwave region, is considered the terahertz region and may probe intermolecular vibrations. The names and classifications of these subregions are conventions, and are only loosely based on the relative molecular or electromagnetic properties.

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Rotational spectroscopy in the context of Electromagnetic absorption by water

The absorption of electromagnetic radiation by water depends on the state of the water.

The absorption in the gas phase occurs in three regions of the spectrum. Rotational transitions are responsible for absorption in the microwave and far-infrared, vibrational transitions in the mid-infrared and near-infrared. Vibrational bands have rotational fine structure. Electronic transitions occur in the vacuum ultraviolet regions.

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Rotational spectroscopy in the context of Rotational–vibrational spectroscopy

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 (or ro-vibrational) transitions. When such transitions emit or absorb photons (electromagnetic radiation), 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.

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