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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.
In chemistry and atomic physics, an electron shell, or principal energy level, may be thought of as the orbit of one or more electrons around an atom's nucleus. The closest shell to the nucleus is called the "1 shell" (also called "K shell"), followed by the "2 shell" (or "L shell"), then the "3 shell" (or "M shell"), and so on farther and farther from the nucleus. The shells correspond with the principal quantum numbers (n = 1, 2, 3, 4 ...) or are labeled alphabetically with letters used in the X-ray notation (K, L, M, N…).
Each shell can contain only a fixed number of electrons: The first shell can hold up to two electrons, the second shell can hold up to eight (2 + 6) electrons, the third shell can hold up to 18 (2 + 6 + 10) and so on. The general formula is that the nth shell can in principle hold up to 2(n2) electrons.Since electrons are electrically attracted to the nucleus, an atom's electrons will generally occupy outer shells only if the more inner shells have already been completely filled by other electrons. However, this is not a strict requirement: atoms may have two or even three incomplete outer shells. (See Madelung rule for more details.) For an explanation of why electrons exist in these shells see electron configuration.
If the potential energy is set to zero at infinite distance from the atomic nucleus or molecule, the usual convention, then bound electron states have negative potential energy.
If an atom, ion, or molecule is at the lowest possible energy level, it and its electrons are said to be in the ground state . If it is at a higher energy level, it is said to be excited , or any electrons that have higher energy than the ground state are excited. If more than one quantum mechanical state is at the same energy, the energy levels are "degenerate". They are then called degenerate energy levels.
Quantized energy levels result from the relation between a particle's energy and its wavelength. For a confined particle such as an electron in an atom, the wave function has the form of standing waves. [ clarification needed ] can exist; for other states the waves interfere destructively,[ clarification needed ] resulting in zero probability density. Elementary examples that show mathematically how energy levels come about are the particle in a box and the quantum harmonic oscillator.Only stationary states with energies corresponding to integral numbers of wavelengths
The first evidence of quantization in atoms was the observation of spectral lines in light from the sun in the early 1800s by Joseph von Fraunhofer and William Hyde Wollaston. The notion of energy levels was proposed in 1913 by Danish physicist Niels Bohr in the Bohr theory of the atom. The modern quantum mechanical theory giving an explanation of these energy levels in terms of the Schrödinger equation was advanced by Erwin Schrödinger and Werner Heisenberg in 1926.
In the formulas for energy of electrons at various levels given below in an atom, the zero point for energy is set when the electron in question has completely left the atom, i.e. when the electron's principal quantum number n = ∞. When the electron is bound to the atom in any closer value of n, the electron's energy is lower and is considered negative.
Assume there is one electron in a given atomic orbital in a hydrogen-like atom (ion). The energy of its state is mainly determined by the electrostatic interaction of the (negative) electron with the (positive) nucleus. The energy levels of an electron around a nucleus are given by :
(typically between 1 eV and 103 eV), where R∞ is the Rydberg constant, Z is the atomic number, n is the principal quantum number, h is Planck's constant, and c is the speed of light. For hydrogen-like atoms (ions) only, the Rydberg levels depend only on the principal quantum number n.
This equation is obtained from combining the Rydberg formula for any hydrogen-like element (shown below) with E = h ν = h c / λ assuming that the principal quantum number n above = n1 in the Rydberg formula and n2 = ∞ (principal quantum number of the energy level the electron descends from, when emitting a photon). The Rydberg formula was derived from empirical spectroscopic emission data.
An equivalent formula can be derived quantum mechanically from the time-independent Schrödinger equation with a kinetic energy Hamiltonian operator using a wave function as an eigenfunction to obtain the energy levels as eigenvalues, but the Rydberg constant would be replaced by other fundamental physics constants.
If there is more than one electron around the atom, electron-electron-interactions raise the energy level. These interactions are often neglected if the spatial overlap of the electron wavefunctions is low.
For multi-electron atoms, interactions between electrons cause the preceding equation to be no longer accurate as stated simply with Z as the atomic number. A simple (though not complete) way to understand this is as a shielding effect, where the outer electrons see an effective nucleus of reduced charge, since the inner electrons are bound tightly to the nucleus and partially cancel its charge. This leads to an approximate correction where Z is substituted with an effective nuclear charge symbolized as Zeff that depends strongly on the principal quantum number.
In such cases, the orbital types (determined by the azimuthal quantum number ℓ) as well as their levels within the molecule affect Zeff and therefore also affect the various atomic electron energy levels. The Aufbau principle of filling an atom with electrons for an electron configuration takes these differing energy levels into account. For filling an atom with electrons in the ground state, the lowest energy levels are filled first and consistent with the Pauli exclusion principle, the Aufbau principle, and Hund's rule.
Fine structure arises from relativistic kinetic energy corrections, spin–orbit coupling (an electrodynamic interaction between the electron's spin and motion and the nucleus's electric field) and the Darwin term (contact term interaction of s shell[ which? ] electrons inside the nucleus). These affect the levels by a typical order of magnitude of 10−3 eV.
This even finer structure is due to electron–nucleus spin–spin interaction, resulting in a typical change in the energy levels by a typical order of magnitude of 10−4 eV.
There is an interaction energy associated with the magnetic dipole moment, μL, arising from the electronic orbital angular momentum, L, given by
Additionally taking into account the magnetic momentum arising from the electron spin.
Due to relativistic effects (Dirac equation), there is a magnetic momentum, μS, arising from the electron spin
with gS the electron-spin g-factor (about 2), resulting in a total magnetic moment, μ,
The interaction energy therefore becomes
Chemical bonds between atoms in a molecule form because they make the situation more stable for the involved atoms, which generally means the sum energy level for the involved atoms in the molecule is lower than if the atoms were not so bonded. As separate atoms approach each other to covalently bond, their orbitals affect each other's energy levels to form bonding and antibonding molecular orbitals. The energy level of the bonding orbitals is lower, and the energy level of the antibonding orbitals is higher. For the bond in the molecule to be stable, the covalent bonding electrons occupy the lower energy bonding orbital, which may be signified by such symbols as σ or π depending on the situation. Corresponding anti-bonding orbitals can be signified by adding an asterisk to get σ* or π* orbitals. A non-bonding orbital in a molecule is an orbital with electrons in outer shells which do not participate in bonding and its energy level is the same as that of the constituent atom. Such orbitals can be designated as n orbitals. The electrons in an n orbital are typically lone pairs.In polyatomic molecules, different vibrational and rotational energy levels are also involved.
Roughly speaking, a molecular energy state, i.e. an eigenstate of the molecular Hamiltonian, is the sum of the electronic, vibrational, rotational, nuclear, and translational components, such that:
where Eelectronic is an eigenvalue of the electronic molecular Hamiltonian (the value of the potential energy surface) at the equilibrium geometry of the molecule.
The molecular energy levels are labelled by the molecular term symbols. The specific energies of these components vary with the specific energy state and the substance.
There are various types of energy level diagrams for bonds between atoms in a molecule.
Electrons in atoms and molecules can change (make transitions in) energy levels by emitting or absorbing a photon (of electromagnetic radiation), whose energy must be exactly equal to the energy difference between the two levels. Electrons can also be completely removed from a chemical species such as an atom, molecule, or ion. Complete removal of an electron from an atom can be a form of ionization, which is effectively moving the electron out to an orbital with an infinite principal quantum number, in effect so far away so as to have practically no more effect on the remaining atom (ion). For various types of atoms, there are 1st, 2nd, 3rd, etc. ionization energies for removing the 1st, then the 2nd, then the 3rd, etc. of the highest energy electrons, respectively, from the atom originally in the ground state. Energy in corresponding opposite quantities can also be released, sometimes in the form of photon energy, when electrons are added to positively charged ions or sometimes atoms. Molecules can also undergo transitions in their vibrational or rotational energy levels. Energy level transitions can also be nonradiative, meaning emission or absorption of a photon is not involved.
If an atom, ion, or molecule is at the lowest possible energy level, it and its electrons are said to be in the ground state . If it is at a higher energy level, it is said to be excited , or any electrons that have higher energy than the ground state are excited. Such a species can be excited to a higher energy level by absorbing a photon whose energy is equal to the energy difference between the levels. Conversely, an excited species can go to a lower energy level by spontaneously emitting a photon equal to the energy difference. A photon's energy is equal to Planck's constant (h) times its frequency (f) and thus is proportional to its frequency, or inversely to its wavelength (λ).
since c, the speed of light, equals to f λ
Correspondingly, many kinds of spectroscopy are based on detecting the frequency or wavelength of the emitted or absorbed photons to provide information on the material analyzed, including information on the energy levels and electronic structure of materials obtained by analyzing the spectrum.
An asterisk is commonly used to designate an excited state. An electron transition in a molecule's bond from a ground state to an excited state may have a designation such as σ → σ*, π → π*, or n → π* meaning excitation of an electron from a σ bonding to a σ antibonding orbital, from a π bonding to a π antibonding orbital, or from an n non-bonding to a π antibonding orbital. Reverse electron transitions for all these types of excited molecules are also possible to return to their ground states, which can be designated as σ* → σ, π* → π, or π* → n.
A transition in an energy level of an electron in a molecule may be combined with a vibrational transition and called a vibronic transition. A vibrational and rotational transition may be combined by rovibrational coupling. In rovibronic coupling, electron transitions are simultaneously combined with both vibrational and rotational transitions. Photons involved in transitions may have energy of various ranges in the electromagnetic spectrum, such as X-ray, ultraviolet, visible light, infrared, or microwave radiation, depending on the type of transition. In a very general way, energy level differences between electronic states are larger, differences between vibrational levels are intermediate, and differences between rotational levels are smaller, although there can be overlap. Translational energy levels are practically continuous and can be calculated as kinetic energy using classical mechanics.
Higher temperature causes fluid atoms and molecules to move faster increasing their translational energy, and thermally excites molecules to higher average amplitudes of vibrational and rotational modes (excites the molecules to higher internal energy levels). This means that as temperature rises, translational, vibrational, and rotational contributions to molecular heat capacity let molecules absorb heat and hold more internal energy. Conduction of heat typically occurs as molecules or atoms collide transferring the heat between each other. At even higher temperatures, electrons can be thermally excited to higher energy orbitals in atoms or molecules. A subsequent drop of an electron to a lower energy level can release a photon, causing a possibly colored glow.
An electron farther from the nucleus has higher potential energy than an electron closer to the nucleus, thus it becomes less bound to the nucleus, since its potential energy is negative and inversely dependent on its distance from the nucleus.
Crystalline solids are found to have energy bands, instead of or in addition to energy levels. Electrons can take on any energy within an unfilled band. At first this appears to be an exception to the requirement for energy levels. However, as shown in band theory, energy bands are actually made up of many discrete energy levels which are too close together to resolve. Within a band the number of levels is of the order of the number of atoms in the crystal, so although electrons are actually restricted to these energies, they appear to be able to take on a continuum of values. The important energy levels in a crystal are the top of the valence band, the bottom of the conduction band, the Fermi level, the vacuum level, and the energy levels of any defect states in the crystal.
In atomic physics, the Bohr model or Rutherford–Bohr model, presented by Niels Bohr and Ernest Rutherford in 1913, is a system consisting of a small, dense nucleus surrounded by orbiting electrons—similar to the structure of the Solar System, but with attraction provided by electrostatic forces in place of gravity. After the cubical model (1902), the plum pudding model (1904), the Saturnian model (1904), and the Rutherford model (1911) came the Rutherford–Bohr model or just Bohr model for short (1913). The improvement over the 1911 Rutherford model mainly concerned the new quantum physical interpretation.
A covalent bond is a chemical bond that involves the sharing of electron pairs between atoms. These electron pairs are known as shared pairs or bonding pairs, and the stable balance of attractive and repulsive forces between atoms, when they share electrons, is known as covalent bonding. For many molecules, the sharing of electrons allows each atom to attain the equivalent of a full outer shell, corresponding to a stable electronic configuration. In organic chemistry, covalent bonds are much more common than ionic bonds.
Diatomic molecules are molecules composed of only two atoms, of the same or different chemical elements. The prefix di- is of Greek origin, meaning "two". If a diatomic molecule consists of two atoms of the same element, such as hydrogen (H2) or oxygen (O2), then it is said to be homonuclear. Otherwise, if a diatomic molecule consists of two different atoms, such as carbon monoxide (CO) or nitric oxide (NO), the molecule is said to be heteronuclear. The bond in a homonuclear diatomic molecule is non-polar.
Spontaneous emission is the process in which a quantum mechanical system transits from an excited energy state to a lower energy state and emits a quantized amount of energy in the form of a photon. Spontaneous emission is ultimately responsible for most of the light we see all around us; it is so ubiquitous that there are many names given to what is essentially the same process. If atoms are excited by some means other than heating, the spontaneous emission is called luminescence. For example, fireflies are luminescent. And there are different forms of luminescence depending on how excited atoms are produced. If the excitation is affected by the absorption of radiation the spontaneous emission is called fluorescence. Sometimes molecules have a metastable level and continue to fluoresce long after the exciting radiation is turned off; this is called phosphorescence. Figurines that glow in the dark are phosphorescent. Lasers start via spontaneous emission, then during continuous operation work by stimulated emission.
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.
In chemistry, a conjugated system is a system of connected p orbitals with delocalized electrons in a molecule, which in general lowers the overall energy of the molecule and increases stability. It is conventionally represented as having alternating single and multiple bonds. Lone pairs, radicals or carbenium ions may be part of the system, which may be cyclic, acyclic, linear or mixed. The term "conjugated" was coined in 1899 by the German chemist Johannes Thiele.
In atomic physics, hyperfine structure is defined by small shifts and splittings in the energy levels of atoms, molecules, and ions, due to interaction between the nucleus and electron clouds.
The Stark effect is the shifting and splitting of spectral lines of atoms and molecules due to the presence of an external electric field. It is the electric-field analogue of the Zeeman effect, where a spectral line is split into several components due to the presence of the magnetic field. Although initially coined for the static case, it is also used in the wider context to describe the effect of time-dependent electric fields. In particular, the Stark effect is responsible for the pressure broadening of spectral lines by charged particles in plasmas. For most spectral lines, the Stark effect is either linear or quadratic with a high accuracy.
Scintillation is a flash of light produced in a transparent material by the passage of a particle. See scintillator and scintillation counter for practical applications.
In physics and chemistry, a selection rule, or transition rule, formally constrains the possible transitions of a system from one quantum state to another. Selection rules have been derived for electromagnetic transitions in molecules, in atoms, in atomic nuclei, and so on. The selection rules may differ according to the technique used to observe the transition. The selection rule also plays a role in chemical reactions, where some are formally spin-forbidden reactions, that is, reactions where the spin state changes at least once from reactants to products.
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.
The Franck–Condon principle is a rule in spectroscopy and quantum chemistry that explains the intensity of vibronic transitions. Vibronic transitions are the simultaneous changes in electronic and vibrational energy levels of a molecule due to the absorption or emission of a photon of the appropriate energy. The principle states that during an electronic transition, a change from one vibrational energy level to another will be more likely to happen if the two vibrational wave functions overlap more significantly.
In atomic physics, the electron magnetic moment, or more specifically the electron magnetic dipole moment, is the magnetic moment of an electron caused by its intrinsic properties of spin and electric charge. The value of the electron magnetic moment is approximately −9.284764×10−24 J/T. The electron magnetic moment has been measured to an accuracy of 7.6 parts in 1013.
In quantum physics, the spin–orbit interaction is a relativistic interaction of a particle's spin with its motion inside a potential. A key example of this phenomenon is the spin–orbit interaction leading to shifts in an electron's atomic energy levels, due to electromagnetic interaction between the electron's magnetic dipole, its orbital motion, and the electrostatic field of the positively charged nucleus. This phenomenon is detectable as a splitting of spectral lines, which can be thought of as a Zeeman effect product of two relativistic effects: the apparent magnetic field seen from the electron perspective and the magnetic moment of the electron associated with its intrinsic spin. A similar effect, due to the relationship between angular momentum and the strong nuclear force, occurs for protons and neutrons moving inside the nucleus, leading to a shift in their energy levels in the nucleus shell model. In the field of spintronics, spin–orbit effects for electrons in semiconductors and other materials are explored for technological applications. The spin–orbit interaction is one cause of magnetocrystalline anisotropy and the spin Hall effect.
A molecular orbital diagram, or MO diagram, is a qualitative descriptive tool explaining chemical bonding in molecules in terms of molecular orbital theory in general and the linear combination of atomic orbitals (LCAO) method in particular. A fundamental principle of these theories is that as atoms bond to form molecules, a certain number of atomic orbitals combine to form the same number of molecular orbitals, although the electrons involved may be redistributed among the orbitals. This tool is very well suited for simple diatomic molecules such as dihydrogen, dioxygen, and carbon monoxide but becomes more complex when discussing even comparatively simple polyatomic molecules, such as methane. MO diagrams can explain why some molecules exist and others do not. They can also predict bond strength, as well as the electronic transitions that can take place.
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.
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.
A non-bonding orbital, also known as non-bonding molecular orbital (NBMO), is a molecular orbital whose occupation by electrons neither increases nor decreases the bond order between the involved atoms. Non-bonding orbitals are often designated by the letter n in molecular orbital diagrams and electron transition notations. Non-bonding orbitals are the equivalent in molecular orbital theory of the lone pairs in Lewis structures. The energy level of a non-bonding orbital is typically in between the lower energy of a valence shell bonding orbital and the higher energy of a corresponding antibonding orbital. As such, a non-bonding orbital with electrons would commonly be a HOMO.
Molecular symmetry in physics and chemistry describes the symmetry present in molecules and the classification of molecules according to their symmetry. Molecular symmetry is a fundamental concept in the application of Quantum Mechanics in physics and chemistry, for example it can be used to predict or explain many of a molecule's properties, such as its dipole moment and its allowed spectroscopic transitions, without doing the exact rigorous calculations. To do this it is necessary to classify the states of the molecule using the irreducible representations from the character table of the symmetry group of the molecule. Among all the molecular symmetries, diatomic molecules show some distinct features and they are relatively easier to analyze.
The helium dimer is a van der Waals molecule with formula He2 consisting of two helium atoms. This chemical is the largest diatomic molecule—a molecule consisting of two atoms bonded together. The bond that holds this dimer together is so weak that it will break if the molecule rotates, or vibrates too much. It can only exist at very low cryogenic temperatures.