Rydberg state

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The Rydberg states [1] of an atom or molecule are electronically excited states with energies that follow the Rydberg formula as they converge on an ionic state with an ionization energy. Although the Rydberg formula was developed to describe atomic energy levels, it has been used to describe many other systems that have electronic structure roughly similar to atomic hydrogen. [2] In general, at sufficiently high principal quantum numbers, an excited electron-ionic core system will have the general character of a hydrogenic system and the energy levels will follow the Rydberg formula. Rydberg states have energies converging on the energy of the ion. The ionization energy threshold is the energy required to completely liberate an electron from the ionic core of an atom or molecule. In practice, a Rydberg wave packet is created by a laser pulse on a hydrogenic atom and thus populates a superposition of Rydberg states. [3] Modern investigations using pump-probe experiments show molecular pathways – e.g. dissociation of (NO)2 – via these special states. [4]

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Rydberg series

Rydberg series describe the energy levels associated with partially removing an electron from the ionic core. Each Rydberg series converges on an ionization energy threshold associated with a particular ionic core configuration. These quantized Rydberg energy levels can be associated with the quasiclassical Bohr atomic picture. The closer you get to the ionization threshold energy, the higher the principal quantum number, and the smaller the energy difference between "near threshold Rydberg states." As the electron is promoted to higher energy levels, the spatial excursion of the electron from the ionic core increases and the system is more like the Bohr quasiclassical picture.

Energy of Rydberg states

The energy of Rydberg states can be refined by including a correction called the quantum defect in the Rydberg formula. The "quantum defect" correction is associated with the presence of a distributed ionic core. Even for many electronically excited molecular systems, the ionic core interaction with an excited electron can take on the general aspects of the interaction between the proton and the electron in the hydrogen atom. The spectroscopic assignment of these states follows the Rydberg formula and they are called Rydberg states of molecules.

Molecular Rydberg states

Although the energy formula of Rydberg series is a result of hydrogen-like atom structure, Rydberg states are also present in molecules. Wave functions of high Rydberg states are very diffuse and span diameters that approach infinity.[ attribution needed ][ vague ] As a result, any isolated neutral molecule behaves like a hydrogen-like atom at the Rydberg limit. For molecules with multiple stable monovalent cations, multiple Rydberg series may exist. Because of the complexity of molecular spectra, low-lying Rydberg states of molecules are often mixed with valence states with similar energy and are thus not pure Rydberg states. [5]

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Related Research Articles

Atomic physics is the field of physics that studies atoms as an isolated system of electrons and an atomic nucleus. Atomic physics typically refers to the study of atomic structure and the interaction between atoms. It is primarily concerned with the way in which electrons are arranged around the nucleus and the processes by which these arrangements change. This comprises ions, neutral atoms and, unless otherwise stated, it can be assumed that the term atom includes ions.

<span class="mw-page-title-main">Bohr model</span> Atomic model introduced by Niels Bohr in 1913

In atomic physics, the Bohr model or Rutherford–Bohr model was the first successful model of the atom. Developed from 1911 to 1918 by Niels Bohr and building on Ernest Rutherford's nuclear model, it supplanted the plum pudding model of J J Thomson only to be replaced by the quantum atomic model in the 1920s. It consists of a small, dense nucleus surrounded by orbiting electrons. It is analogous to the structure of the Solar System, but with attraction provided by electrostatic force rather than gravity, and with the electron energies quantized.

Atomic, molecular, and optical physics (AMO) is the study of matter–matter and light–matter interactions, at the scale of one or a few atoms and energy scales around several electron volts. The three areas are closely interrelated. AMO theory includes classical, semi-classical and quantum treatments. Typically, the theory and applications of emission, absorption, scattering of electromagnetic radiation (light) from excited atoms and molecules, analysis of spectroscopy, generation of lasers and masers, and the optical properties of matter in general, fall into these categories.

<span class="mw-page-title-main">Energy level</span> Different states of quantum systems

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.

<span class="mw-page-title-main">Ionization</span> Process by which atoms or molecules acquire charge by gaining or losing electrons

Ionization is the process by which an atom or a molecule acquires a negative or positive charge by gaining or losing electrons, often in conjunction with other chemical changes. The resulting electrically charged atom or molecule is called an ion. Ionization can result from the loss of an electron after collisions with subatomic particles, collisions with other atoms, molecules, electrons, positrons, protons, antiprotons and ions, or through the interaction with electromagnetic radiation. Heterolytic bond cleavage and heterolytic substitution reactions can result in the formation of ion pairs. Ionization can occur through radioactive decay by the internal conversion process, in which an excited nucleus transfers its energy to one of the inner-shell electrons causing it to be ejected.

<span class="mw-page-title-main">Electron configuration</span> Mode of arrangement of electrons in different shells of an atom

In atomic physics and quantum chemistry, the electron configuration is the distribution of electrons of an atom or molecule in atomic or molecular orbitals. For example, the electron configuration of the neon atom is 1s2 2s2 2p6, meaning that the 1s, 2s, and 2p subshells are occupied by two, two, and six electrons, respectively.

<span class="mw-page-title-main">Rydberg formula</span> Formula for spectral line wavelengths in alkali metals

In atomic physics, the Rydberg formula calculates the wavelengths of a spectral line in many chemical elements. The formula was primarily presented as a generalization of the Balmer series for all atomic electron transitions of hydrogen. It was first empirically stated in 1888 by the Swedish physicist Johannes Rydberg, then theoretically by Niels Bohr in 1913, who used a primitive form of quantum mechanics. The formula directly generalizes the equations used to calculate the wavelengths of the hydrogen spectral series.

<span class="mw-page-title-main">Emission spectrum</span> Frequencies of light emitted by atoms or chemical compounds

The emission spectrum of a chemical element or chemical compound is the spectrum of frequencies of electromagnetic radiation emitted due to electrons making a transition from a high energy state to a lower energy state. The photon energy of the emitted photons is equal to the energy difference between the two states. There are many possible electron transitions for each atom, and each transition has a specific energy difference. This collection of different transitions, leading to different radiated wavelengths, make up an emission spectrum. Each element's emission spectrum is unique. Therefore, spectroscopy can be used to identify elements in matter of unknown composition. Similarly, the emission spectra of molecules can be used in chemical analysis of substances.

<span class="mw-page-title-main">Excited state</span> Quantum states with more energy than the lowest possible amount

In quantum mechanics, an excited state of a system is any quantum state of the system that has a higher energy than the ground state. Excitation refers to an increase in energy level above a chosen starting point, usually the ground state, but sometimes an already excited state. The temperature of a group of particles is indicative of the level of excitation.

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<span class="mw-page-title-main">Molecular physics</span> Study of the physical and chemical properties of molecules

Molecular physics is the study of the physical properties of molecules and molecular dynamics. The field overlaps significantly with physical chemistry, chemical physics, and quantum chemistry. It is often considered as a sub-field of atomic, molecular, and optical physics. Research groups studying molecular physics are typically designated as one of these other fields. Molecular physics addresses phenomena due to both molecular structure and individual atomic processes within molecules. Like atomic physics, it relies on a combination of classical and quantum mechanics to describe interactions between electromagnetic radiation and matter. Experiments in the field often rely heavily on techniques borrowed from atomic physics, such as spectroscopy and scattering.

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<span class="mw-page-title-main">Rydberg atom</span> Excited atomic quantum state with high principal quantum number (n)

A Rydberg atom is an excited atom with one or more electrons that have a very high principal quantum number, n. The higher the value of n, the farther the electron is from the nucleus, on average. Rydberg atoms have a number of peculiar properties including an exaggerated response to electric and magnetic fields, long decay periods and electron wavefunctions that approximate, under some conditions, classical orbits of electrons about the nuclei. The core electrons shield the outer electron from the electric field of the nucleus such that, from a distance, the electric potential looks identical to that experienced by the electron in a hydrogen atom.

<span class="mw-page-title-main">Hydrogen spectral series</span> Important atomic emission spectra

The emission spectrum of atomic hydrogen has been divided into a number of spectral series, with wavelengths given by the Rydberg formula. These observed spectral lines are due to the electron making transitions between two energy levels in an atom. The classification of the series by the Rydberg formula was important in the development of quantum mechanics. The spectral series are important in astronomical spectroscopy for detecting the presence of hydrogen and calculating red shifts.

Rydberg ionization spectroscopy is a spectroscopy technique in which multiple photons are absorbed by an atom causing the removal of an electron to form an ion.

A Rydberg molecule is an electronically excited chemical species. Electronically excited molecular states are generally quite different in character from electronically excited atomic states. However, particularly for highly electronically excited molecular systems, the ionic core interaction with an excited electron can take on the general aspects of the interaction between the proton and the electron in the hydrogen atom. The spectroscopic assignment of these states follows the Rydberg formula, named after the Swedish physicist Johannes Rydberg, and they are called Rydberg states of molecules. Rydberg series are associated with partially removing an electron from the ionic core.

A heavy Rydberg system consists of a weakly bound positive and negative ion orbiting their common centre of mass. Such systems share many properties with the conventional Rydberg atom and consequently are sometimes referred to as heavy Rydberg atoms. While such a system is a type of ionically bound molecule, it should not be confused with a molecular Rydberg state, which is simply a molecule with one or more highly excited electrons.

Photoelectrochemical processes are processes in photoelectrochemistry; they usually involve transforming light into other forms of energy. These processes apply to photochemistry, optically pumped lasers, sensitized solar cells, luminescence, and photochromism.

Triatomic hydrogen or H3 is an unstable triatomic molecule containing only hydrogen. Since this molecule contains only three atoms of hydrogen it is the simplest triatomic molecule and it is relatively simple to numerically solve the quantum mechanics description of the particles. Being unstable the molecule breaks up in under a millionth of a second. Its fleeting lifetime makes it rare, but it is quite commonly formed and destroyed in the universe thanks to the commonness of the trihydrogen cation. The infrared spectrum of H3 due to vibration and rotation is very similar to that of the ion, H+
3
. In the early universe this ability to emit infrared light allowed the primordial hydrogen and helium gas to cool down so as to form stars.

Bond softening is an effect of reducing the strength of a chemical bond by strong laser fields. To make this effect significant, the strength of the electric field in the laser light has to be comparable with the electric field the bonding electron "feels" from the nuclei of the molecule. Such fields are typically in the range of 1–10 V/Å, which corresponds to laser intensities 1013–1015 W/cm2. Nowadays, these intensities are routinely achievable from table-top Ti:Sapphire lasers.

References

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