A hydrogen atom is an
atom
Atoms are the basic particles of the chemical elements. An atom consists of a atomic nucleus, nucleus of protons and generally neutrons, surrounded by an electromagnetically bound swarm of electrons. The chemical elements are distinguished fr ...
of the
chemical element
A chemical element is a chemical substance whose atoms all have the same number of protons. The number of protons is called the atomic number of that element. For example, oxygen has an atomic number of 8: each oxygen atom has 8 protons in its ...
hydrogen
Hydrogen is a chemical element; it has chemical symbol, symbol H and atomic number 1. It is the lightest and abundance of the chemical elements, most abundant chemical element in the universe, constituting about 75% of all baryon, normal matter ...
. The
electrically neutral hydrogen atom contains a single positively charged
proton
A proton is a stable subatomic particle, symbol , Hydron (chemistry), H+, or 1H+ with a positive electric charge of +1 ''e'' (elementary charge). Its mass is slightly less than the mass of a neutron and approximately times the mass of an e ...
in the nucleus, and a single negatively charged
electron
The electron (, or in nuclear reactions) is a subatomic particle with a negative one elementary charge, elementary electric charge. It is a fundamental particle that comprises the ordinary matter that makes up the universe, along with up qua ...
bound to the nucleus by the
Coulomb force. Atomic hydrogen constitutes
about 75% of the
baryon
In particle physics, a baryon is a type of composite particle, composite subatomic particle that contains an odd number of valence quarks, conventionally three. proton, Protons and neutron, neutrons are examples of baryons; because baryons are ...
ic mass of the universe.
In everyday life on Earth, isolated hydrogen atoms (called "atomic hydrogen") are extremely rare. Instead, a hydrogen atom tends to combine with other atoms in compounds, or with another hydrogen atom to form ordinary (
diatomic
Diatomic molecules () are molecules composed of only two atoms, of the same or different chemical elements. If a diatomic molecule consists of two atoms of the same element, such as hydrogen () or oxygen (), then it is said to be homonuclear mol ...
) hydrogen gas, H
2. "Atomic hydrogen" and "hydrogen atom" in ordinary English use have overlapping, yet distinct, meanings. For example, a water molecule contains two hydrogen atoms, but does not contain atomic hydrogen (which would refer to isolated hydrogen atoms).
Atomic spectroscopy shows that there is a discrete infinite set of states in which a hydrogen (or any) atom can exist, contrary to the predictions of
classical physics
Classical physics refers to physics theories that are non-quantum or both non-quantum and non-relativistic, depending on the context. In historical discussions, ''classical physics'' refers to pre-1900 physics, while '' modern physics'' refers to ...
. Attempts to develop a theoretical understanding of the states of the hydrogen atom have been important to the
history of quantum mechanics
The history of quantum mechanics is a fundamental part of the History of physics#20th century: birth of modern physics, history of modern physics. The major chapters of this history begin with the emergence of quantum ideas to explain individual ...
, since all other atoms can be roughly understood by knowing in detail about this simplest atomic structure.
Isotopes
The most
abundant isotope
Isotopes are distinct nuclear species (or ''nuclides'') of the same chemical element. They have the same atomic number (number of protons in their Atomic nucleus, nuclei) and position in the periodic table (and hence belong to the same chemica ...
, protium (
1H), or light hydrogen, contains no
neutron
The neutron is a subatomic particle, symbol or , that has no electric charge, and a mass slightly greater than that of a proton. The Discovery of the neutron, neutron was discovered by James Chadwick in 1932, leading to the discovery of nucle ...
s and is simply a
proton
A proton is a stable subatomic particle, symbol , Hydron (chemistry), H+, or 1H+ with a positive electric charge of +1 ''e'' (elementary charge). Its mass is slightly less than the mass of a neutron and approximately times the mass of an e ...
and an
electron
The electron (, or in nuclear reactions) is a subatomic particle with a negative one elementary charge, elementary electric charge. It is a fundamental particle that comprises the ordinary matter that makes up the universe, along with up qua ...
. Protium is
stable
A stable is a building in which working animals are kept, especially horses or oxen. The building is usually divided into stalls, and may include storage for equipment and feed.
Styles
There are many different types of stables in use tod ...
and makes up 99.985% of naturally occurring hydrogen atoms.
Deuterium
Deuterium (hydrogen-2, symbol H or D, also known as heavy hydrogen) is one of two stable isotopes of hydrogen; the other is protium, or hydrogen-1, H. The deuterium nucleus (deuteron) contains one proton and one neutron, whereas the far more c ...
(
2H) contains one neutron and one proton in its nucleus. Deuterium is stable, makes up 0.0156% of naturally occurring hydrogen,
and is used in industrial processes like
nuclear reactor
A nuclear reactor is a device used to initiate and control a Nuclear fission, fission nuclear chain reaction. They are used for Nuclear power, commercial electricity, nuclear marine propulsion, marine propulsion, Weapons-grade plutonium, weapons ...
s and
Nuclear Magnetic Resonance
Nuclear magnetic resonance (NMR) is a physical phenomenon in which nuclei in a strong constant magnetic field are disturbed by a weak oscillating magnetic field (in the near field) and respond by producing an electromagnetic signal with a ...
.
Tritium
Tritium () or hydrogen-3 (symbol T or H) is a rare and radioactive isotope of hydrogen with a half-life of ~12.33 years. The tritium nucleus (t, sometimes called a ''triton'') contains one proton and two neutrons, whereas the nucleus of the ...
(
3H) contains two neutrons and one proton in its nucleus and is not stable, decaying with a
half-life Half-life is a mathematical and scientific description of exponential or gradual decay.
Half-life, half life or halflife may also refer to:
Film
* Half-Life (film), ''Half-Life'' (film), a 2008 independent film by Jennifer Phang
* ''Half Life: ...
of 12.32 years. Because of its short half-life, tritium does not exist in nature except in trace amounts.
Heavier isotopes of hydrogen are only created artificially in
particle accelerators
A particle accelerator is a machine that uses electromagnetic fields to propel electric charge, charged particles to very high speeds and energies to contain them in well-defined particle beam, beams. Small accelerators are used for fundamental ...
and have half-lives on the order of 10
−22 seconds. They are unbound
resonances
Resonance is a phenomenon that occurs when an object or system is subjected to an external force or vibration whose frequency matches a resonant frequency (or resonance frequency) of the system, defined as a frequency that generates a maximu ...
located beyond the
neutron drip line; this results in prompt
emission of a neutron.
The formulas below are valid for all three isotopes of hydrogen, but slightly different values of the
Rydberg constant (correction formula given below) must be used for each hydrogen isotope.
Hydrogen ion
Lone neutral hydrogen atoms are rare under normal conditions. However, neutral hydrogen is common when it is
covalently bound to another atom, and hydrogen atoms can also exist in
cationic and anionic forms.
If a neutral hydrogen atom loses its electron, it becomes a cation. The resulting ion, which consists solely of a proton for the usual isotope, is written as "H
+" and sometimes called ''
hydron''. Free protons are common in the
interstellar medium
The interstellar medium (ISM) is the matter and radiation that exists in the outer space, space between the star systems in a galaxy. This matter includes gas in ionic, atomic, and molecular form, as well as cosmic dust, dust and cosmic rays. It f ...
, and
solar wind
The solar wind is a stream of charged particles released from the Sun's outermost atmospheric layer, the Stellar corona, corona. This Plasma (physics), plasma mostly consists of electrons, protons and alpha particles with kinetic energy betwee ...
. In the context of
aqueous solution
An aqueous solution is a solution in which the solvent is water. It is mostly shown in chemical equations by appending (aq) to the relevant chemical formula. For example, a solution of table salt, also known as sodium chloride (NaCl), in water ...
s of classical
Brønsted–Lowry acids, such as
hydrochloric acid
Hydrochloric acid, also known as muriatic acid or spirits of salt, is an aqueous solution of hydrogen chloride (HCl). It is a colorless solution with a distinctive pungency, pungent smell. It is classified as a acid strength, strong acid. It is ...
, it is actually
hydronium
In chemistry, hydronium (hydroxonium in traditional British English) is the cation , also written as , the type of oxonium ion produced by protonation of water. It is often viewed as the positive ion present when an Arrhenius acid is dissolved ...
,
H3 O+, that is meant. Instead of a literal ionized single hydrogen atom being formed, the acid transfers the hydrogen to H
2O, forming H
3O
+.
If instead a hydrogen atom gains a second electron, it becomes an anion. The
hydrogen anion is written as "H
–" and called ''
hydride
In chemistry, a hydride is formally the anion of hydrogen (H−), a hydrogen ion with two electrons. In modern usage, this is typically only used for ionic bonds, but it is sometimes (and has been more frequently in the past) applied to all che ...
''.
Theoretical analysis
The hydrogen atom has special significance in
quantum mechanics
Quantum mechanics is the fundamental physical Scientific theory, theory that describes the behavior of matter and of light; its unusual characteristics typically occur at and below the scale of atoms. Reprinted, Addison-Wesley, 1989, It is ...
and
quantum field theory
In theoretical physics, quantum field theory (QFT) is a theoretical framework that combines Field theory (physics), field theory and the principle of relativity with ideas behind quantum mechanics. QFT is used in particle physics to construct phy ...
as a simple
two-body problem physical system which has yielded many simple
analytical solutions in closed-form.
Failed classical description
Experiments
An experiment is a procedure carried out to support or refute a hypothesis, or determine the efficacy or likelihood of something previously untried. Experiments provide insight into Causality, cause-and-effect by demonstrating what outcome o ...
by
Ernest Rutherford
Ernest Rutherford, 1st Baron Rutherford of Nelson (30 August 1871 – 19 October 1937) was a New Zealand physicist who was a pioneering researcher in both Atomic physics, atomic and nuclear physics. He has been described as "the father of nu ...
in 1909 showed the structure of the atom to be a dense, positive nucleus with a tenuous negative charge cloud around it. This immediately raised questions about how such a system could be stable.
Classical electromagnetism
Classical electromagnetism or classical electrodynamics is a branch of physics focused on the study of interactions between electric charges and electrical current, currents using an extension of the classical Newtonian model. It is, therefore, a ...
had shown that any accelerating charge radiates energy, as shown by the
Larmor formula. If the electron is assumed to orbit in a perfect circle and radiates energy continuously, the electron would rapidly spiral into the nucleus with a fall time of:
where
is the
Bohr radius and
is the
classical electron radius
The classical electron radius is a combination of fundamental Physical quantity, physical quantities that define a length scale for problems involving an electron interacting with electromagnetic radiation. It links the classical electrostatic sel ...
. If this were true, all atoms would instantly collapse. However, atoms seem to be stable. Furthermore, the spiral inward would release a smear of electromagnetic frequencies as the orbit got smaller. Instead, atoms were observed to emit only discrete frequencies of radiation. The resolution would lie in the development of
quantum mechanics
Quantum mechanics is the fundamental physical Scientific theory, theory that describes the behavior of matter and of light; its unusual characteristics typically occur at and below the scale of atoms. Reprinted, Addison-Wesley, 1989, It is ...
.
Bohr–Sommerfeld Model
In 1913,
Niels Bohr
Niels Henrik David Bohr (, ; ; 7 October 1885 – 18 November 1962) was a Danish theoretical physicist who made foundational contributions to understanding atomic structure and old quantum theory, quantum theory, for which he received the No ...
obtained the energy levels and spectral frequencies of the hydrogen atom after making a number of simple assumptions in order to correct the failed classical model. The assumptions included:
# Electrons can only be in certain, discrete circular orbits or ''stationary states'', thereby having a discrete set of possible radii and energies.
# Electrons do not emit radiation while in one of these stationary states.
# An electron can gain or lose energy by jumping from one discrete orbit to another.
Bohr supposed that the electron's angular momentum is quantized with possible values:
where
and
is
Planck constant
The Planck constant, or Planck's constant, denoted by h, is a fundamental physical constant of foundational importance in quantum mechanics: a photon's energy is equal to its frequency multiplied by the Planck constant, and the wavelength of a ...
over
. He also supposed that the
centripetal force
Centripetal force (from Latin ''centrum'', "center" and ''petere'', "to seek") is the force that makes a body follow a curved trajectory, path. The direction of the centripetal force is always orthogonality, orthogonal to the motion of the bod ...
which keeps the electron in its orbit is provided by the
Coulomb force, and that energy is conserved. Bohr derived the energy of each orbit of the hydrogen atom to be:
where
is the
electron mass
In particle physics, the electron mass (symbol: ) is the mass of a stationary electron, also known as the invariant mass of the electron. It is one of the fundamental constants of physics. It has a value of about or about , which has an energy ...
,
is the
electron charge,
is the
vacuum permittivity
Vacuum permittivity, commonly denoted (pronounced "epsilon nought" or "epsilon zero"), is the value of the absolute dielectric permittivity of classical vacuum. It may also be referred to as the permittivity of free space, the electric const ...
, and
is the
quantum number
In quantum physics and chemistry, quantum numbers are quantities that characterize the possible states of the system.
To fully specify the state of the electron in a hydrogen atom, four quantum numbers are needed. The traditional set of quantu ...
(now known as the
principal quantum number
In quantum mechanics, the principal quantum number (''n'') of an electron in an atom indicates which electron shell or energy level it is in. Its values are natural numbers (1, 2, 3, ...).
Hydrogen and Helium, at their lowest energies, have just ...
). Bohr's predictions matched experiments measuring the
hydrogen spectral series to the first order, giving more confidence to a theory that used quantized values.
For
, the value
[Eite Tiesinga, Peter J. Mohr, David B. Newell, and Barry N. Taylor (2019), "The 2018 CODATA Recommended Values of the Fundamental Physical Constants" (Web Version 8.0). Database developed by J. Baker, M. Douma, and S. Kotochigova. Available at http://physics.nist.gov/constants, National Institute of Standards and Technology, Gaithersburg, MD 20899]
Link to R∞
Link to hcR∞
/ref>
is called the Rydberg unit of energy. It is related to the Rydberg constant of atomic physics
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 wit ...
by
The exact value of the Rydberg constant assumes that the nucleus is infinitely massive with respect to the electron. For hydrogen-1, hydrogen-2 (deuterium
Deuterium (hydrogen-2, symbol H or D, also known as heavy hydrogen) is one of two stable isotopes of hydrogen; the other is protium, or hydrogen-1, H. The deuterium nucleus (deuteron) contains one proton and one neutron, whereas the far more c ...
), and hydrogen-3 (tritium
Tritium () or hydrogen-3 (symbol T or H) is a rare and radioactive isotope of hydrogen with a half-life of ~12.33 years. The tritium nucleus (t, sometimes called a ''triton'') contains one proton and two neutrons, whereas the nucleus of the ...
) which have finite mass, the constant must be slightly modified to use the reduced mass of the system, rather than simply the mass of the electron. This includes the kinetic energy of the nucleus in the problem, because the total (electron plus nuclear) kinetic energy is equivalent to the kinetic energy of the reduced mass moving with a velocity equal to the electron velocity relative to the nucleus. However, since the nucleus is much heavier than the electron, the electron mass and reduced mass are nearly the same. The Rydberg constant ''RM'' for a hydrogen atom (one electron), ''R'' is given by
where is the mass of the atomic nucleus. For hydrogen-1, the quantity is about 1/1836 (i.e. the electron-to-proton mass ratio). For deuterium and tritium, the ratios are about 1/3670 and 1/5497 respectively. These figures, when added to 1 in the denominator, represent very small corrections in the value of ''R'', and thus only small corrections to all energy levels in corresponding hydrogen isotopes.
There were still problems with Bohr's model:
# it failed to predict other spectral details such as fine structure and hyperfine structure
# it could only predict energy levels with any accuracy for single–electron atoms (hydrogen-like atoms)
# the predicted values were only correct to , where is the fine-structure constant
In physics, the fine-structure constant, also known as the Sommerfeld constant, commonly denoted by (the Alpha, Greek letter ''alpha''), is a Dimensionless physical constant, fundamental physical constant that quantifies the strength of the el ...
.
Most of these shortcomings were resolved by Arnold Sommerfeld's modification of the Bohr model. Sommerfeld introduced two additional degrees of freedom, allowing an electron to move on an elliptical orbit characterized by its eccentricity
Eccentricity or eccentric may refer to:
* Eccentricity (behavior), odd behavior on the part of a person, as opposed to being "normal"
Mathematics, science and technology Mathematics
* Off-Centre (geometry), center, in geometry
* Eccentricity (g ...
and declination
In astronomy, declination (abbreviated dec; symbol ''δ'') is one of the two angles that locate a point on the celestial sphere in the equatorial coordinate system, the other being hour angle. The declination angle is measured north (positive) or ...
with respect to a chosen axis. This introduced two additional quantum numbers, which correspond to the orbital angular momentum
Angular momentum (sometimes called moment of momentum or rotational momentum) is the rotational analog of Momentum, linear momentum. It is an important physical quantity because it is a Conservation law, conserved quantity – the total ang ...
and its projection on the chosen axis. Thus the correct multiplicity of states (except for the factor 2 accounting for the yet unknown electron spin) was found. Further, by applying special relativity
In physics, the special theory of relativity, or special relativity for short, is a scientific theory of the relationship between Spacetime, space and time. In Albert Einstein's 1905 paper, Annus Mirabilis papers#Special relativity,
"On the Ele ...
to the elliptic orbits, Sommerfeld succeeded in deriving the correct expression for the fine structure of hydrogen spectra (which happens to be exactly the same as in the most elaborate Dirac theory). However, some observed phenomena, such as the anomalous Zeeman effect
The Zeeman effect () is the splitting of a spectral line into several components in the presence of a static magnetic field. It is caused by the interaction of the magnetic field with the magnetic moment of the atomic electron associated with ...
, remained unexplained. These issues were resolved with the full development of quantum mechanics and the Dirac equation
In particle physics, the Dirac equation is a relativistic wave equation derived by British physicist Paul Dirac in 1928. In its free form, or including electromagnetic interactions, it describes all spin-1/2 massive particles, called "Dirac ...
. It is often alleged that the Schrödinger equation
The Schrödinger equation is a partial differential equation that governs the wave function of a non-relativistic quantum-mechanical system. Its discovery was a significant landmark in the development of quantum mechanics. It is named after E ...
is superior to the Bohr–Sommerfeld theory in describing hydrogen atom. This is not the case, as most of the results of both approaches coincide or are very close (a remarkable exception is the problem of hydrogen atom in crossed electric and magnetic fields, which cannot be self-consistently solved in the framework of the Bohr–Sommerfeld theory), and in both theories the main shortcomings result from the absence of the electron spin. It was the complete failure of the Bohr–Sommerfeld theory to explain many-electron systems (such as helium atom or hydrogen molecule) which demonstrated its inadequacy in describing quantum phenomena.
Schrödinger equation
The Schrödinger equation is the standard quantum-mechanics model; it allows one to calculate the stationary states and also the time evolution of quantum systems. Exact analytical answers are available for the nonrelativistic hydrogen atom. Before we go to present a formal account, here we give an elementary overview.
Given that the hydrogen atom contains a nucleus and an electron, quantum mechanics allows one to predict the probability of finding the electron at any given radial distance . It is given by the square of a mathematical function known as the "wavefunction
In quantum physics, a wave function (or wavefunction) is a mathematical description of the quantum state of an isolated quantum system. The most common symbols for a wave function are the Greek letters and (lower-case and capital psi (letter) ...
", which is a solution of the Schrödinger equation. The lowest energy equilibrium state of the hydrogen atom is known as the ground state. The ground state wave function is known as the wavefunction. It is written as:
Here, is the numerical value of the Bohr radius. The probability density of finding the electron at a distance in any radial direction is the squared value of the wavefunction:
The wavefunction is spherically symmetric, and the surface area of a shell at distance is , so the total probability of the electron being in a shell at a distance and thickness is
It turns out that this is a maximum at . That is, the Bohr picture of an electron orbiting the nucleus at radius corresponds to the most probable radius. Actually, there is a finite probability that the electron may be found at any place , with the
probability indicated by the square of the wavefunction. Since the probability of finding the electron ''somewhere'' in the whole volume is unity, the integral of is unity. Then we say that the wavefunction is properly normalized.
As discussed below, the ground state is also indicated by the quantum numbers
In Quantum mechanics, quantum physics and chemistry, quantum numbers are quantities that characterize the possible states of the system.
To fully specify the state of the electron in a hydrogen atom, four quantum numbers are needed. The traditi ...
. The second lowest energy states, just above the ground state, are given by the quantum numbers , , and . These states all have the same energy and are known as the and states. There is one state:
and there are three states:
An electron in the or state is most likely to be found in the second Bohr orbit with energy given by the Bohr formula.
Wavefunction
The Hamiltonian
Hamiltonian may refer to:
* Hamiltonian mechanics, a function that represents the total energy of a system
* Hamiltonian (quantum mechanics), an operator corresponding to the total energy of that system
** Dyall Hamiltonian, a modified Hamiltonian ...
of the hydrogen atom is the radial kinetic energy operator plus the Coulomb electrostatic potential energy between the positive proton and the negative electron. Using the time-independent Schrödinger equation, ignoring all spin-coupling interactions and using the reduced mass , the equation is written as:
Expanding the Laplacian
In mathematics, the Laplace operator or Laplacian is a differential operator given by the divergence of the gradient of a scalar function on Euclidean space. It is usually denoted by the symbols \nabla\cdot\nabla, \nabla^2 (where \nabla is th ...
in spherical coordinates:
This is a separable, partial differential equation
In mathematics, a partial differential equation (PDE) is an equation which involves a multivariable function and one or more of its partial derivatives.
The function is often thought of as an "unknown" that solves the equation, similar to ho ...
which can be solved in terms of special functions. When the wavefunction is separated as product of functions , , and three independent differential functions appears with A and B being the separation constants:
* radial:
* polar:
* azimuth:
The normalized position wavefunction
In quantum physics, a wave function (or wavefunction) is a mathematical description of the quantum state of an isolated quantum system. The most common symbols for a wave function are the Greek letters and (lower-case and capital psi (letter) ...
s, given in spherical coordinates are:
where:
* ,
* is the reduced Bohr radius, ,
* is a generalized Laguerre polynomial of degree , and
* is a spherical harmonic function of degree and order .
Note that the generalized Laguerre polynomials are defined differently by different authors. The usage here is consistent with the definitions used by Messiah, and Mathematica. In other places, the Laguerre polynomial includes a factor of , or the generalized Laguerre polynomial appearing in the hydrogen wave function is instead.
The quantum numbers can take the following values:
* (principal quantum number
In quantum mechanics, the principal quantum number (''n'') of an electron in an atom indicates which electron shell or energy level it is in. Its values are natural numbers (1, 2, 3, ...).
Hydrogen and Helium, at their lowest energies, have just ...
)
* (azimuthal quantum number
In quantum mechanics, the azimuthal quantum number is a quantum number for an atomic orbital that determines its angular momentum operator, orbital angular momentum and describes aspects of the angular shape of the orbital. The azimuthal quantum ...
)
* (magnetic quantum number
In atomic physics, a magnetic quantum number is a quantum number used to distinguish quantum states of an electron or other particle according to its angular momentum along a given axis in space. The orbital magnetic quantum number ( or ) disting ...
).
Additionally, these wavefunctions are ''normalized'' (i.e., the integral of their modulus square equals 1) and orthogonal
In mathematics, orthogonality (mathematics), orthogonality is the generalization of the geometric notion of ''perpendicularity''. Although many authors use the two terms ''perpendicular'' and ''orthogonal'' interchangeably, the term ''perpendic ...
:
where is the state represented by the wavefunction in Dirac notation
Paul Adrien Maurice Dirac ( ; 8 August 1902 – 20 October 1984) was an English mathematician and Theoretical physics, theoretical physicist who is considered to be one of the founders of quantum mechanics. Dirac laid the foundations for bot ...
, and is the Kronecker delta
In mathematics, the Kronecker delta (named after Leopold Kronecker) is a function of two variables, usually just non-negative integers. The function is 1 if the variables are equal, and 0 otherwise:
\delta_ = \begin
0 &\text i \neq j, \\
1 &\ ...
function.
The wavefunctions in momentum space are related to the wavefunctions in position space through a Fourier transform
which, for the bound states, results in
where denotes a Gegenbauer polynomial and is in units of .
The solutions to the Schrödinger equation for hydrogen are analytical, giving a simple expression for the hydrogen energy levels
A quantum mechanics, quantum mechanical system or particle that is bound state, bound—that is, confined spatially—can only take on certain discrete values of energy, called energy levels. This contrasts with classical mechanics, classical pa ...
and thus the frequencies of the hydrogen spectral line
A spectral line is a weaker or stronger region in an otherwise uniform and continuous spectrum. It may result from emission (electromagnetic radiation), emission or absorption (electromagnetic radiation), absorption of light in a narrow frequency ...
s and fully reproduced the Bohr model and went beyond it. It also yields two other quantum numbers and the shape of the electron's wave function ("orbital") for the various possible quantum-mechanical states, thus explaining the anisotropic
Anisotropy () is the structural property of non-uniformity in different directions, as opposed to isotropy. An anisotropic object or pattern has properties that differ according to direction of measurement. For example, many materials exhibit ver ...
character of atomic bonds.
The Schrödinger equation also applies to more complicated atoms and molecule
A molecule is a group of two or more atoms that are held together by Force, attractive forces known as chemical bonds; depending on context, the term may or may not include ions that satisfy this criterion. In quantum physics, organic chemi ...
s. When there is more than one electron or nucleus the solution is not analytical and either computer calculations are necessary or simplifying assumptions must be made.
Since the Schrödinger equation is only valid for non-relativistic quantum mechanics, the solutions it yields for the hydrogen atom are not entirely correct. The Dirac equation
In particle physics, the Dirac equation is a relativistic wave equation derived by British physicist Paul Dirac in 1928. In its free form, or including electromagnetic interactions, it describes all spin-1/2 massive particles, called "Dirac ...
of relativistic quantum theory improves these solutions (see below).
Results of Schrödinger equation
The solution of the Schrödinger equation (wave equation) for the hydrogen atom uses the fact that the Coulomb potential produced by the nucleus is isotropic
In physics and geometry, isotropy () is uniformity in all orientations. Precise definitions depend on the subject area. Exceptions, or inequalities, are frequently indicated by the prefix ' or ', hence '' anisotropy''. ''Anisotropy'' is also ...
(it is radially symmetric in space and only depends on the distance to the nucleus). Although the resulting energy eigenfunctions (the ''orbitals'') are not necessarily isotropic themselves, their dependence on the angular coordinates follows completely generally from this isotropy of the underlying potential: the eigenstates of the Hamiltonian
Hamiltonian may refer to:
* Hamiltonian mechanics, a function that represents the total energy of a system
* Hamiltonian (quantum mechanics), an operator corresponding to the total energy of that system
** Dyall Hamiltonian, a modified Hamiltonian ...
(that is, the energy eigenstates) can be chosen as simultaneous eigenstates of the angular momentum operator
In quantum mechanics, the angular momentum operator is one of several related operators analogous to classical angular momentum. The angular momentum operator plays a central role in the theory of atomic and molecular physics and other quantum pro ...
. This corresponds to the fact that angular momentum is conserved in the orbital motion
In celestial mechanics, an orbit (also known as orbital revolution) is the curved trajectory of an object such as the trajectory of a planet around a star, or of a natural satellite around a planet, or of an artificial satellite around an obj ...
of the electron around the nucleus. Therefore, the energy eigenstates may be classified by two angular momentum quantum number
In quantum physics and chemistry, quantum numbers are quantities that characterize the possible states of the system.
To fully specify the state of the electron in a hydrogen atom, four quantum numbers are needed. The traditional set of quantu ...
s, and (both are integers). The angular momentum quantum number determines the magnitude of the angular momentum. The magnetic quantum number determines the projection of the angular momentum on the (arbitrarily chosen) -axis.
In addition to mathematical expressions for total angular momentum and angular momentum projection of wavefunctions, an expression for the radial dependence of the wave functions must be found. It is only here that the details of the Coulomb potential enter (leading to Laguerre polynomials in ). This leads to a third quantum number, the principal quantum number . The principal quantum number in hydrogen is related to the atom's total energy.
Note that the maximum value of the angular momentum quantum number is limited by the principal quantum number: it can run only up to , i.e., .
Due to angular momentum conservation, states of the same but different have the same energy (this holds for all problems with rotational symmetry
Rotational symmetry, also known as radial symmetry in geometry, is the property a shape (geometry), shape has when it looks the same after some rotation (mathematics), rotation by a partial turn (angle), turn. An object's degree of rotational s ...
). In addition, for the hydrogen atom, states of the same but different are also degenerate (i.e., they have the same energy). However, this is a specific property of hydrogen and is no longer true for more complicated atoms which have an (effective) potential differing from the form (due to the presence of the inner electrons shielding the nucleus potential).
Taking into account the spin of the electron adds a last quantum number, the projection of the electron's spin angular momentum along the -axis, which can take on two values. Therefore, any eigenstate of the electron in the hydrogen atom is described fully by four quantum numbers. According to the usual rules of quantum mechanics, the actual state of the electron may be any superposition of these states. This explains also why the choice of -axis for the directional quantization of the angular momentum vector is immaterial: an orbital of given and obtained for another preferred axis can always be represented as a suitable superposition of the various states of different (but same ) that have been obtained for .
Mathematical summary of eigenstates of hydrogen atom
In 1928, Paul Dirac
Paul Adrien Maurice Dirac ( ; 8 August 1902 – 20 October 1984) was an English mathematician and Theoretical physics, theoretical physicist who is considered to be one of the founders of quantum mechanics. Dirac laid the foundations for bot ...
found an equation that was fully compatible with special relativity
In physics, the special theory of relativity, or special relativity for short, is a scientific theory of the relationship between Spacetime, space and time. In Albert Einstein's 1905 paper, Annus Mirabilis papers#Special relativity,
"On the Ele ...
, and (as a consequence) made the wave function a 4-component "Dirac spinor
In quantum field theory, the Dirac spinor is the spinor that describes all known fundamental particles that are fermions, with the possible exception of neutrinos. It appears in the plane-wave solution to the Dirac equation, and is a certain comb ...
" including "up" and "down" spin components, with both positive and "negative" energy (or matter and antimatter). The solution to this equation gave the following results, more accurate than the Schrödinger solution.
=Energy levels
=
The energy levels of hydrogen, including fine structure (excluding Lamb shift
In physics, the Lamb shift, named after Willis Lamb, is an anomalous difference in energy between two electron orbitals in a hydrogen atom. The difference was not predicted by theory and it cannot be derived from the Dirac equation, which pre ...
and hyperfine structure), are given by the Sommerfeld fine-structure expression:[GermanEnglish]
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where is the fine-structure constant
In physics, the fine-structure constant, also known as the Sommerfeld constant, commonly denoted by (the Alpha, Greek letter ''alpha''), is a Dimensionless physical constant, fundamental physical constant that quantifies the strength of the el ...
and is the total angular momentum quantum number, which is equal to , depending on the orientation of the electron spin relative to the orbital angular momentum. This formula represents a small correction to the energy obtained by Bohr and Schrödinger as given above. The factor in square brackets in the last expression is nearly one; the extra term arises from relativistic effects (for details, see #Features going beyond the Schrödinger solution). It is worth noting that this expression was first obtained by A. Sommerfeld in 1916 based on the relativistic version of the old Bohr theory. Sommerfeld has however used different notation for the quantum numbers.
Visualizing the hydrogen electron orbitals
The image to the right shows the first few hydrogen atom orbitals (energy eigenfunctions). These are cross-sections of the probability density that are color-coded (black represents zero density and white represents the highest density). The angular momentum (orbital) quantum number ''ℓ'' is denoted in each column, using the usual spectroscopic letter code (''s'' means ''ℓ'' = 0, ''p'' means ''ℓ'' = 1, ''d'' means ''ℓ'' = 2). The main (principal) quantum number ''n'' (= 1, 2, 3, ...) is marked to the right of each row. For all pictures the magnetic quantum number ''m'' has been set to 0, and the cross-sectional plane is the ''xz''-plane (''z'' is the vertical axis). The probability density in three-dimensional space is obtained by rotating the one shown here around the ''z''-axis.
The "ground state
The ground state of a quantum-mechanical system is its stationary state of lowest energy; the energy of the ground state is known as the zero-point energy of the system. An excited state is any state with energy greater than the ground state ...
", i.e. the state of lowest energy, in which the electron is usually found, is the first one, the 1''s'' state ( principal quantum level ''n'' = 1, ''ℓ'' = 0).
Black lines occur in each but the first orbital: these are the nodes of the wavefunction, i.e. where the probability density is zero. (More precisely, the nodes are spherical harmonics
In mathematics and physical science, spherical harmonics are special functions defined on the surface of a sphere. They are often employed in solving partial differential equations in many scientific fields. The table of spherical harmonics co ...
that appear as a result of solving the Schrödinger equation
The Schrödinger equation is a partial differential equation that governs the wave function of a non-relativistic quantum-mechanical system. Its discovery was a significant landmark in the development of quantum mechanics. It is named after E ...
in spherical coordinates.)
The quantum number
In quantum physics and chemistry, quantum numbers are quantities that characterize the possible states of the system.
To fully specify the state of the electron in a hydrogen atom, four quantum numbers are needed. The traditional set of quantu ...
s determine the layout of these nodes. There are:
* total nodes,
* of which are angular nodes:
** angular nodes go around the axis (in the ''xy'' plane). (The figure above does not show these nodes since it plots cross-sections through the ''xz''-plane.)
** (the remaining angular nodes) occur on the (vertical) axis.
* (the remaining non-angular nodes) are radial nodes.
Oscillation of orbitals
The frequency of a state in level n is , so in case of a superposition of multiple orbitals, they would oscillate due to the difference in frequency. For example two states, ψ1and ψ2: The wavefunction is given by and the probability function is
The result is a rotating wavefunction. The movement of electrons and change of quantum states radiates light at a frequency of the cosine.
Features going beyond the Schrödinger solution
There are several important effects that are neglected by the Schrödinger equation and which are responsible for certain small but measurable deviations of the real spectral lines from the predicted ones:
* Although the mean speed of the electron in hydrogen is only 1/137th of the speed of light
The speed of light in vacuum, commonly denoted , is a universal physical constant exactly equal to ). It is exact because, by international agreement, a metre is defined as the length of the path travelled by light in vacuum during a time i ...
, many modern experiments are sufficiently precise that a complete theoretical explanation requires a fully relativistic treatment of the problem. A relativistic treatment results in a momentum increase of about 1 part in 37,000 for the electron. Since the electron's wavelength is determined by its momentum, orbitals containing higher speed electrons show contraction due to smaller wavelengths.
* Even when there is no external magnetic field
A magnetic field (sometimes called B-field) is a physical field that describes the magnetic influence on moving electric charges, electric currents, and magnetic materials. A moving charge in a magnetic field experiences a force perpendicular ...
, in the inertial frame
In classical physics and special relativity, an inertial frame of reference (also called an inertial space or a Galilean reference frame) is a frame of reference in which objects exhibit inertia: they remain at rest or in uniform motion relative ...
of the moving electron, the electromagnetic field of the nucleus has a magnetic component. The spin of the electron has an associated magnetic moment
In electromagnetism, the magnetic moment or magnetic dipole moment is the combination of strength and orientation of a magnet or other object or system that exerts a magnetic field. The magnetic dipole moment of an object determines the magnitude ...
which interacts with this magnetic field. This effect is also explained by special relativity, and it leads to the so-called '' spin–orbit coupling'', i.e., an interaction between the electron
The electron (, or in nuclear reactions) is a subatomic particle with a negative one elementary charge, elementary electric charge. It is a fundamental particle that comprises the ordinary matter that makes up the universe, along with up qua ...
's orbital motion
In celestial mechanics, an orbit (also known as orbital revolution) is the curved trajectory of an object such as the trajectory of a planet around a star, or of a natural satellite around a planet, or of an artificial satellite around an obj ...
around the nucleus, and its spin.
Both of these features (and more) are incorporated in the relativistic Dirac equation
In particle physics, the Dirac equation is a relativistic wave equation derived by British physicist Paul Dirac in 1928. In its free form, or including electromagnetic interactions, it describes all spin-1/2 massive particles, called "Dirac ...
, with predictions that come still closer to experiment. Again the Dirac equation may be solved analytically in the special case of a two-body system, such as the hydrogen atom. The resulting solution quantum states now must be classified by the total angular momentum number (arising through the coupling between electron spin and orbital angular momentum). States of the same and the same are still degenerate. Thus, direct analytical solution of Dirac equation
In particle physics, the Dirac equation is a relativistic wave equation derived by British physicist Paul Dirac in 1928. In its free form, or including electromagnetic interactions, it describes all spin-1/2 massive particles, called "Dirac ...
predicts 2S() and 2P() levels of hydrogen to have exactly the same energy, which is in a contradiction with observations ( Lamb–Retherford experiment).
* There are always vacuum fluctuations of the electromagnetic field
An electromagnetic field (also EM field) is a physical field, varying in space and time, that represents the electric and magnetic influences generated by and acting upon electric charges. The field at any point in space and time can be regarde ...
, according to quantum mechanics. Due to such fluctuations degeneracy between states of the same but different is lifted, giving them slightly different energies. This has been demonstrated in the famous Lamb–Retherford experiment and was the starting point for the development of the theory of quantum electrodynamics
In particle physics, quantum electrodynamics (QED) is the Theory of relativity, relativistic quantum field theory of electrodynamics. In essence, it describes how light and matter interact and is the first theory where full agreement between quant ...
(which is able to deal with these vacuum fluctuations and employs the famous Feynman diagrams for approximations using perturbation theory
In mathematics and applied mathematics, perturbation theory comprises methods for finding an approximate solution to a problem, by starting from the exact solution of a related, simpler problem. A critical feature of the technique is a middle ...
). This effect is now called Lamb shift
In physics, the Lamb shift, named after Willis Lamb, is an anomalous difference in energy between two electron orbitals in a hydrogen atom. The difference was not predicted by theory and it cannot be derived from the Dirac equation, which pre ...
.
For these developments, it was essential that the solution of the Dirac equation for the hydrogen atom could be worked out exactly, such that any experimentally observed deviation had to be taken seriously as a signal of failure of the theory.
Alternatives to the Schrödinger theory
In the language of Heisenberg's matrix mechanics, the hydrogen atom was first solved by Wolfgang Pauli
Wolfgang Ernst Pauli ( ; ; 25 April 1900 – 15 December 1958) was an Austrian theoretical physicist and a pioneer of quantum mechanics. In 1945, after having been nominated by Albert Einstein, Pauli received the Nobel Prize in Physics "for the ...
[
] using a rotational symmetry
Rotational symmetry, also known as radial symmetry in geometry, is the property a shape (geometry), shape has when it looks the same after some rotation (mathematics), rotation by a partial turn (angle), turn. An object's degree of rotational s ...
in four dimensions (4)-symmetrygenerated by the angular momentum
Angular momentum (sometimes called moment of momentum or rotational momentum) is the rotational analog of Momentum, linear momentum. It is an important physical quantity because it is a Conservation law, conserved quantity – the total ang ...
and the Laplace–Runge–Lenz vector. By extending the symmetry group O(4) to the dynamical group O(4,2),
the entire spectrum and all transitions were embedded in a single irreducible group representation.
In 1979 the (non-relativistic) hydrogen atom was solved for the first time within Feynman's path integral formulation
The path integral formulation is a description in quantum mechanics that generalizes the stationary action principle of classical mechanics. It replaces the classical notion of a single, unique classical trajectory for a system with a sum, or ...
of quantum mechanics
Quantum mechanics is the fundamental physical Scientific theory, theory that describes the behavior of matter and of light; its unusual characteristics typically occur at and below the scale of atoms. Reprinted, Addison-Wesley, 1989, It is ...
by Duru and Kleinert.[
] This work greatly extended the range of applicability of Feynman's method.
Further alternative models are Bohm mechanics and the complex Hamilton-Jacobi formulation of quantum mechanics.
See also
* Antihydrogen
Antihydrogen () is the antimatter counterpart of hydrogen. Whereas the common hydrogen atom is composed of an electron and proton, the antihydrogen atom is made up of a positron and antiproton. Scientists hope that studying antihydrogen may sh ...
* Atomic orbital
In quantum mechanics, an atomic orbital () is a Function (mathematics), function describing the location and Matter wave, wave-like behavior of an electron in an atom. This function describes an electron's Charge density, charge distribution a ...
* Balmer series
* Helium atom
A helium atom is an atom of the chemical element helium. Helium is composed of two electrons bound by the electromagnetic force to a nucleus containing two protons along with two neutrons, depending on the isotope, held together by the strong ...
* Hydrogen molecular ion
* List of quantum-mechanical systems with analytical solutions
* Lithium atom
* Proton decay
* Quantum chemistry
Quantum chemistry, also called molecular quantum mechanics, is a branch of physical chemistry focused on the application of quantum mechanics to chemical systems, particularly towards the quantum-mechanical calculation of electronic contributions ...
* Quantum state
In quantum physics, a quantum state is a mathematical entity that embodies the knowledge of a quantum system. Quantum mechanics specifies the construction, evolution, and measurement of a quantum state. The result is a prediction for the system ...
* Trihydrogen cation
References
Books
* Section 4.2 deals with the hydrogen atom specifically, but all of Chapter 4 is relevant.
* Kleinert, H. (2009). ''Path Integrals in Quantum Mechanics, Statistics, Polymer Physics, and Financial Markets'', 4th edition
Worldscibooks.com
World Scientific, Singapore (also available onlin
External links
* ttp://scienceworld.wolfram.com/physics/HydrogenAtom.html Physics of hydrogen atom on Scienceworld
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Atoms
Quantum models
Hydrogen
Hydrogen physics
Isotopes of hydrogen
Exactly solvable models
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