Editing Lewis structure

{{short description|Diagrams for the bonding between atoms of a molecule and lone pairs of electrons}}
[[File:Freie Elektronenpaare Wasser V3.svg|class=skin-invert-image|alt=A lewis structure of a water molecule, composed of two hydrogen atoms and one oxygen atom sharing valence electrons|thumb|Lewis structure of a [[properties of water|water molecule]]]]

'''Lewis structures'''{{snd}}also called '''Lewis dot formulas''', '''Lewis dot structures''', '''electron dot structures''', or '''Lewis electron dot structures''' ('''LEDs'''){{snd}}are diagrams that show the [[chemical bond|bonding]] between [[atom]]s of a [[molecule]], as well as the [[lone pair]]s of [[electron]]s that may exist in the molecule.<ref>[http://goldbook.iupac.org/L03513.html IUPAC definition of Lewis formula]</ref><ref>Zumdahl, S. (2005) ''Chemical Principles'' Houghton-Mifflin ({{ISBN|0-618-37206-7}})</ref><ref>{{citation |author1=G.L. Miessler |author2=D.A. Tarr |year=2003 |title=Inorganic Chemistry |edition=2nd |publisher=Pearson Prentice–Hall |isbn=0-13-035471-6 |url-access=registration |url=https://archive.org/details/inorganicchemist03edmies }}</ref> Introduced by [[Gilbert N. Lewis]] in his 1916 article ''The Atom and the Molecule'', a Lewis structure can be drawn for any [[covalent]]ly bonded molecule, as well as [[complex (chemistry)|coordination compounds]]. <ref>{{citation |author=Lewis, G. N. |title=The Atom and the Molecule |journal=J. Am. Chem. Soc. |year=1916 |volume=38 |issue=4 |pages=762–85 |doi=10.1021/ja02261a002|bibcode=1916JAChS..38..762L |s2cid=95865413 |url=https://zenodo.org/record/1429068 }}</ref> Lewis structures extend the concept of the '''electron dot diagram''' by adding lines between atoms to represent [[shared pair]]s in a chemical bond.

Lewis structures show each atom and its position in the structure of the molecule using its chemical symbol. Lines are drawn between atoms that are bonded to one another (pairs of dots can be used instead of lines). Excess electrons that form lone pairs are represented as pairs of dots, and are placed next to the atoms.

Although [[main group element]]s of the [[Period 2 element|second period]] and beyond usually react by gaining, losing, or sharing electrons until they have achieved a valence shell electron configuration with a full [[octet rule|octet]] of (8) electrons, [[hydrogen]] instead obeys the [[duplet rule]], forming one bond for a complete valence shell of two electrons.

== Construction and electron counting ==
{{Main article|Electron counting}}
[[File:Ammonia Lewis structure.svg|class=skin-invert-image|thumb|Comparison between electron dot diagrams and Lewis structure]]
For a neutral molecule, the total number of electrons represented in a Lewis structure is equal to the sum of the numbers of [[valence electron]]s on each individual atom, not the maximum possible. Non-valence electrons are not represented in Lewis structures as they do not bond.

Once the total number of valence electrons has been determined, they are placed into the structure according to these steps:
# Initially, one line (representing a single bond) is drawn between each pair of connected atoms.
# Each bond consists of a pair of electrons, so if ''t'' is the total number of electrons to be placed and ''n'' is the number of single bonds just drawn, ''t''&minus;2''n'' electrons remain to be placed. These are temporarily drawn as dots, one per electron, to a maximum of eight per atom (two in the case of hydrogen), minus two for each bond.
# Electrons are distributed first to the outer atoms and then to the others, until there are no more to be placed.
# Finally, each atom (other than hydrogen) that is surrounded by fewer than eight electrons (counting each bond as two) is processed as follows: For every two electrons needed, two dots are deleted from a neighboring atom and an additional line is drawn between the two atoms. This represents the conversion of a lone pair of electrons into a bonding pair, which adds two electrons to the former atom's valence shell while leaving the latter's electron count unchanged.
# In the preceding steps, if there are not enough electrons to fill the valence shells of all atoms, preference is given to those atoms whose electronegativity is higher.

Lewis structures for polyatomic ions may be drawn by the same method. However when counting electrons, negative ions should have extra electrons placed in their Lewis structures; positive ions should have fewer electrons than an uncharged molecule. When the Lewis structure of an ion is written, the entire structure is placed in brackets, and the charge is written as a superscript on the upper right, outside the brackets.

===Miburo method===
A simpler method has been proposed for constructing Lewis structures, eliminating the need for electron counting: the atoms are drawn showing the valence electrons; bonds are then formed by pairing up valence electrons of the atoms involved in the bond-making process, and anions and cations are formed by adding or removing electrons to/from the appropriate atoms.<ref>{{citation |author=Miburo, Barnabe B. |year=1993 |title=Simplified Lewis Structure Drawing for Non-science Majors |journal=[[J. Chem. Educ.]] |volume=75 |issue=3 |page=317 |doi=10.1021/ed075p317|bibcode=1998JChEd..75..317M }}</ref>

A trick is to count up valence electrons, then count up the number of electrons needed to complete the octet rule (or with hydrogen just 2 electrons), then take the difference of these two numbers. The answer is the number of electrons that make up the bonds. The rest of the electrons just go to fill all the other atoms' octets.

===Lever method===
Another simple and general procedure to write Lewis structures and resonance forms has been proposed.<ref>{{citation |author=Lever, A. B. P. |year=1972 |title=Lewis Structures and the Octet Rule |journal=[[J. Chem. Educ.]] |volume=49 |issue=12 |page=819 |doi=10.1021/ed049p819|bibcode=1972JChEd..49..819L }}</ref>{{example needed|date=March 2025}}

This system works in nearly all cases, however there are 3 instances where it will not work{{citation needed|date=October 2024}}. These exceptions are outlined in the table below.
{| class="wikitable"
|+ Exceptions
|-
! The Exception !! How it Breaks the System !! How to Fix the Lewis Structure
|-
| Free Radicals (molecules with unpaired valence electrons) || Sum of TVe will be an odd number. Bond number will not be a whole number.|| Round calculated bond number down to the nearest whole number. (e.g. 4.5 bonds would round down to 4 bonds)
|-
| Valence Shell Deficiency || Does not break the system, must instead memorize when it occurs.|| BeX<sub>2</sub>, BX<sub>3</sub>, and AlX<sub>3</sub>. "X" represents Hydrogen or Halogens. When Be is bonded with 2 other atoms, or when B and Al are bonded with 3 other atoms, they do not form full valence shells. Assume single bonds and use the actual bond number to calculate lone pairs.
|-
| Expanded Octet (only occurs for elements in Groups 3-8)|| Bond calculation will provide too few bonds for the number of atoms in the molecule.|| Assume single bonds, use the minimum number of bonds necessary to create the molecule.
|}

== Formal charge ==
{{Main article|Formal charge}}
In terms of Lewis structures, [[formal charge]] is used in the description, comparison, and assessment of likely [[topology|topological]] and [[Resonance (chemistry)|resonance]] structures<ref name="miessler_1">Miessler, G. L. and Tarr, D. A., ''Inorganic Chemistry'' (2nd ed., Prentice Hall 1998) {{ISBN|0-13-841891-8}}, pp. 49–53 – Explanation of formal charge usage.</ref> by determining the apparent electronic charge of each atom within, based upon its electron dot structure, assuming exclusive covalency or [[non-polar]] bonding. It has uses in determining possible electron re-configuration when referring to [[reaction mechanism]]s, and often results in the same sign as the [[partial charge]] of the atom, with exceptions. In general, the formal charge of an atom can be calculated using the following formula, assuming non-standard definitions for the markup used:

:<math>C_f = N_v - U_e - \frac {B_n} 2 </math>
where:
* <math>C_f</math> is the formal charge.
* <math>N_v</math> represents the number of valence electrons in a free atom of the element.
* <math>U_e</math> represents the number of unshared electrons on the atom.
* <math>B_n</math> represents the total number of electrons in bonds the atom has with another.

The formal charge of an atom is computed as the difference between the number of valence electrons that a neutral atom would have and the number of electrons that belong to it in the Lewis structure. Electrons in covalent bonds are split equally between the atoms involved in the bond. The total of the formal charges on an ion should be equal to the charge on the ion, and the total of the formal charges on a neutral molecule should be equal to zero.

== Resonance ==
{{Main article|Resonance structure}}
For some molecules and ions, it is difficult to determine which lone pairs should be moved to form double or triple bonds, and two or more different ''resonance'' structures may be written for the same molecule or ion. In such cases it is usual to write all of them with two-way arrows in between {{xref|(see {{slink||Example}} below)}}. This is sometimes the case when multiple atoms of the same type surround the central atom, and is especially common for polyatomic ions.

When this situation occurs, the molecule's Lewis structure is said to be a [[Resonance (chemistry)|resonance structure]], and the molecule exists as a resonance hybrid. Each of the different possibilities is superimposed on the others, and the molecule is considered to have a Lewis structure equivalent to some combination of these states.

The nitrate ion ({{chem2|NO3−}}), for instance, must form a double bond between nitrogen and one of the oxygens to satisfy the octet rule for nitrogen. However, because the molecule is symmetrical, it does not matter ''which'' of the oxygens forms the double bond. In this case, there are three possible resonance structures. Expressing resonance when drawing Lewis structures may be done either by drawing each of the possible resonance forms and placing double-headed arrows between them or by using dashed lines to represent the partial bonds (although the latter is a good representation of the resonance hybrid which is not, formally speaking, a Lewis structure).

When comparing resonance structures for the same molecule, usually those with the fewest formal charges contribute more to the overall resonance hybrid. When formal charges are necessary, resonance structures that have negative charges on the more electronegative elements and positive charges on the less electronegative elements are favored.

Single bonds can also be moved in the same way to create resonance structures for [[hypervalent molecules]] such as [[sulfur hexafluoride]], which is the correct description according to quantum chemical calculations instead of the common expanded octet model.

The resonance structure should not be interpreted to indicate that the molecule switches between forms, but that the molecule acts as the average of multiple forms.

== Example ==
The formula of the [[nitrite]] ion is {{chem2|NO2−}}.

# Nitrogen is the least electronegative atom of the two, so it is the central atom by multiple criteria.
# Count valence electrons. Nitrogen has 5 valence electrons; each oxygen has 6, for a total of (6 × 2) + 5 = 17. The ion has a charge of −1, which indicates an extra electron, so the total number of electrons is 18.
# Connect the atoms by single bonds. Each oxygen must be bonded to the nitrogen, which uses four electrons—two in each bond.
# Place lone pairs. The 14 remaining electrons should initially be placed as 7 lone pairs. Each oxygen may take a maximum of 3 lone pairs, giving each oxygen 8 electrons including the bonding pair. The seventh lone pair must be placed on the nitrogen atom.
# Satisfy the octet rule. Both oxygen atoms currently have 8 electrons assigned to them. The nitrogen atom has only 6 electrons assigned to it. One of the lone pairs on an oxygen atom must form a double bond, but either atom will work equally well. Therefore, there is a resonance structure.
# Tie up loose ends. Two Lewis structures must be drawn: Each structure has one of the two oxygen atoms double-bonded to the nitrogen atom. The second oxygen atom in each structure will be single-bonded to the nitrogen atom. Place brackets around each structure, and add the charge (−) to the upper right outside the brackets. Draw a double-headed arrow between the two resonance forms.

[[File:Nitrite-ion-lewis-canonical.svg|class=skin-invert-image|center|500px]]

== Alternative formations ==
<div class="skin-invert" style="color:black;">{{Image frame|width=200|caption=Two varieties of condensed structural formula, both showing [[butane]]
|content=<math chem>\begin{matrix}
\ce{CH3-CH2-CH2-CH3}\\
\ce{CH3CH2CH2CH3}
\end{matrix}</math>}}</div>
[[File:Butane-skeletal.png|class=skin-invert-image|thumb|right|200px|A skeletal diagram of [[butane]]]]
Chemical structures may be written in more compact forms, particularly when showing [[organic compound|organic molecules]]. In condensed structural formulas, many or even all of the covalent bonds may be left out, with subscripts indicating the number of identical groups attached to a particular atom.
Another shorthand structural diagram is the [[skeletal formula]] (also known as a bond-line formula or carbon skeleton diagram). In a skeletal formula, carbon atoms are not signified by the symbol C but by the [[vertex (graph theory)|vertices]] of the lines. Hydrogen atoms bonded to carbon are not shown—they can be inferred by counting the number of bonds to a particular carbon atom—each carbon is assumed to have four bonds in total, so any bonds not shown are, by implication, to hydrogen atoms.

Other diagrams may be more complex than Lewis structures, showing bonds in 3D using various forms such as [[space-filling diagram]]s.

== Usage and limitations ==
Despite their simplicity and development in the early twentieth century, when understanding of chemical bonding was still rudimentary, Lewis structures capture many of the key features of the electronic structure of a range of molecular systems, including those of relevance to chemical reactivity. Thus, they continue to enjoy widespread use by chemists and chemistry educators. This is especially true in the field of [[organic chemistry]], where the traditional valence-bond model of bonding still dominates, and mechanisms are often understood in terms of [[Arrow pushing|curve-arrow notation]] superimposed upon [[Skeletal formula|skeletal formulae]], which are shorthand versions of Lewis structures. Due to the greater variety of bonding schemes encountered in [[Inorganic chemistry|inorganic]] and [[organometallic chemistry]], many of the molecules encountered require the use of fully delocalized [[Molecular orbital|molecular orbitals]] to adequately describe their bonding, making Lewis structures comparatively less important (although they are still common).

There are simple and archetypal molecular systems for which a Lewis description, at least in unmodified form, is misleading or inaccurate. Notably, the naive drawing of Lewis structures for molecules known experimentally to contain unpaired electrons (e.g., O<sub>2</sub>, NO, and ClO<sub>2</sub>) leads to incorrect inferences of bond orders, bond lengths, and/or magnetic properties. A simple Lewis model also does not account for the phenomenon of [[aromaticity]]. For instance, Lewis structures do not offer an explanation for why cyclic C<sub>6</sub>H<sub>6</sub> (benzene) experiences special stabilization beyond normal delocalization effects, while C<sub>4</sub>H<sub>4</sub> (cyclobutadiene) actually experiences a special ''destabilization''.{{cn|date=December 2023}}  [[Molecular orbital theory]] provides the most straightforward explanation for these phenomena.{{original research inline|date=December 2023}}

== See also ==
* [[VSEPR theory|Valence shell electron pair repulsion theory]]
* [[Molecular geometry]]
* [[Structural formula]]
* [[Natural bond orbital]]
{{clear}}

== References ==
{{reflist|30em}}

== External links ==
*  [http://hyperphysics.phy-astr.gsu.edu/hbase/pertab/perlewis.html Lewis Dot Diagrams of Selected Elements]
*  [https://lewistructure.com/ Lewis structures for all compounds]

{{Molecular visualization}}
{{Chemical bonding theory}}

[[Category:1916 introductions]]
[[Category:Chemical formulas]]
[[Category:Chemical bonding]]