1823:
1073:
31:
1087:
1817:
1829:
200:, in condensed matter (liquids and solids), the effect is cumulative over the volume of materials, or within and between organic molecules, such that London dispersion forces can be quite strong in bulk solid and liquids and decay much more slowly with distance. For example, the total force per unit area between two bulk solids decreases by
891:). The "explanation" of the dispersion force as the interaction between two such dipoles was invented after London arrived at the proper quantum mechanical theory. The authoritative work contains a criticism of the instantaneous dipole model and a modern and thorough exposition of the theory of intermolecular forces.
439:
because the terms in this series can be regarded as energies of two interacting multipoles, one on each monomer. Substitution of the multipole-expanded form of V into the second-order energy yields an expression that resembles an expression describing the interaction between instantaneous multipoles
143:, the interaction is essentially instantaneous and is described in terms of a "non-retarded" Hamaker constant. For entities that are farther apart, the finite time required for the fluctuation at one atom to be felt at a second atom ("retardation") requires use of a "retarded" Hamaker constant.
906:
Dispersion forces are usually dominant over the three van der Waals forces (orientation, induction, dispersion) between atoms and molecules, with the exception of molecules that are small and highly polar, such as water. The following contribution of the dispersion to the total intermolecular
96:
The electron distribution around an atom or molecule undergoes fluctuations in time. These fluctuations create instantaneous electric fields which are felt by other nearby atoms and molecules, which in turn adjust the spatial distribution of their own electrons. The net effect is that the
882:
365:
between the electrons and nuclei of the two moieties (atoms or molecules). The second-order perturbation expression of the interaction energy contains a sum over states. The states appearing in this sum are simple products of the stimulated electronic states of the
286:
from the gas phase into the liquid or solid phase. Sublimation heats of e.g. hydrocarbon crystals reflect the dispersion interaction. Liquification of oxygen and nitrogen gases into liquid phases is also dominated by attractive London dispersion forces.
97:
fluctuations in electron positions in one atom induce a corresponding redistribution of electrons in other atoms, such that the electron motions become correlated. While the detailed theory requires a quantum-mechanical explanation
898:, which is why London coined the phrase "dispersion effect". In physics, the term "dispersion" describes the variation of a quantity with frequency, which is the fluctuation of the electrons in the case of the London dispersion.
730:
309:. The polarizability is a measure of how easily electrons can be redistributed; a large polarizability implies that the electrons are more easily redistributed. This trend is exemplified by the
548:
329:). The same increase of dispersive attraction occurs within and between organic molecules in the order RF, RCl, RBr, RI (from smallest to largest) or with other more polarizable
232:
198:
648:
618:
17:
406:
471:
702:
675:
722:
588:
568:
495:
426:
252:
164:
137:
1916:
80:
that are normally electrically symmetric; that is, the electrons are symmetrically distributed with respect to the nucleus. They are part of the
254:
is the separation between them. The effects of London dispersion forces are most obvious in systems that are very non-polar (e.g., that lack
298:
molecules. That is, the instantaneous fluctuations in one atom or molecule are felt both by the solvent (water) and by other molecules.
345:
at room temperature, bromine is a liquid, and iodine is a solid. The London forces are thought to arise from the motion of electrons.
301:
Larger and heavier atoms and molecules exhibit stronger dispersion forces than smaller and lighter ones. This is due to the increased
115:) attract each other. The magnitude of the London dispersion force is frequently described in terms of a single parameter called the
2034:
1961:
1642:
358:
294:, the effects of dispersion forces between atoms or molecules are frequently less pronounced due to competition with polarizable
1406:
R. Eisenschitz & F. London (1930), "Über das Verhältnis der van der
Waalsschen Kräfte zu den homöopolaren Bindungskräften",
1345:
1242:
1210:
877:{\displaystyle E_{AB}^{\rm {disp}}\approx -{3 \over 2}{I_{A}I_{B} \over I_{A}+I_{B}}{\alpha '_{A}\alpha '_{B} \over {R^{6}}}}
146:
While the London dispersion force between individual atoms and molecules is quite weak and decreases quickly with separation
1956:
1492:
1278:
1169:
1144:
1881:
290:
When atoms/molecules are separated by a third medium (rather than vacuum), the situation becomes more complex. In
1705:
1299:
Wagner, J.P.; Schreiner, P.R. (2015), "London dispersion in molecular chemistry — reconsidering steric effects",
1896:
1390:
Schneider,Hans-Jörg
Dispersive Interactions in Solution Complexes Dispersive Interactions in Solution Complexes
2060:
1732:
1693:
1683:
1688:
1635:
507:
203:
169:
140:
2065:
1951:
1941:
1931:
1906:
1876:
1115:
371:
384:
1722:
623:
593:
1983:
1886:
1628:
888:
1225:
Gelardi, G.; Flatt, R.J. (2016), "Working mechanisms of water reducers and superplasticizers",
1110:
1100:
451:
2027:
1988:
2022:
1395:
1946:
1837:
1700:
1659:
1525:
1457:
1415:
1370:
680:
653:
498:
370:. Thus, no intermolecular antisymmetrization of the electronic states is included, and the
69:
8:
1848:
1712:
1678:
1606:
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895:
436:
362:
81:
2012:
1529:
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1234:
1202:
1193:
Israelachvili, Jacob N. (2011), "Interactions of
Biological Membranes and Structures",
707:
573:
553:
504:
In this manner, the following approximation is obtained for the dispersion interaction
480:
444:, must be introduced in order to obtain a description of London dispersion in terms of
411:
237:
149:
122:
441:
1998:
1787:
1747:
1737:
1498:
1488:
1477:
1435:
1316:
1274:
1238:
1206:
1175:
1165:
1140:
952:
474:
440:(see the qualitative description above). Additionally, an approximation, named after
38:
2039:
1779:
1752:
1559:
1533:
1465:
1423:
1334:
1308:
1266:
1230:
1198:
1078:
963:
291:
116:
1159:
2017:
1891:
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887:
Note that this final London equation does not contain instantaneous dipoles (see
306:
107:
1926:
1727:
1092:
445:
429:
302:
911:
Contribution of the dispersion to the total intermolecular interaction energy
2054:
1975:
1935:
1868:
1822:
1797:
1670:
1651:
1502:
1162:
Fundamentals of materials science and engineering : an interactive etext
985:
378:
353:
The first explanation of the attraction between noble gas atoms was given by
1179:
62:
instantaneous dipole–induced dipole forces, fluctuating induced dipole bonds
1921:
1510:
1320:
1312:
354:
283:
85:
1137:
Fundamentals of
Materials Science and Engineering: An Interactive e . Text
894:
The London theory has much similarity to the quantum mechanical theory of
2007:
1757:
1575:
1563:
259:
255:
1516:
Parr, Robert G. (2001), "Quantum
Chemistry: Classic Scientific Papers",
30:
1469:
1427:
650:
are the polarizability volumes of the respective atoms. The quantities
330:
1537:
1742:
1717:
1448:
London, F. (1930), "Zur
Theorie und Systematik der Molekularkräfte",
1816:
1086:
338:
334:
77:
1620:
1004:
935:
367:
310:
295:
263:
271:
112:
1160:
Callister, William D. Jr.; Callister, William D. Jr. (2001).
1021:
35:
1550:
F. London (1937), "The general theory of molecular forces",
41:. The long-range section is due to London dispersion forces.
1576:
J. O. Hirschfelder; C. F. Curtiss & R. B. Bird (1954),
924:
73:
1828:
1259:"The theory of molecular attractive forces between solids"
342:
279:
105:, the effect is frequently described as the formation of
1405:
139:. For atoms that are located closer together than the
357:
in 1930. He used a quantum-mechanical theory based on
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240:
206:
172:
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125:
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are the first ionization energies of the atoms, and
1605:
1333:Karlström, Gunnar; Jönsson, Bo (6 February 2013).
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696:
669:
642:
612:
582:
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420:
400:
278:a solid at room temperature). In hydrocarbons and
246:
226:
192:
158:
131:
1256:
2052:
1332:
282:, the dispersion forces are sufficient to cause
1298:
101:quantum mechanical theory of dispersion forces
100:
84:. The LDF is named after the German physicist
18:Instantaneous-dipole induced-dipole attraction
1636:
1227:Science and Technology of Concrete Admixtures
1192:
88:. They are the weakest intermolecular force.
1485:Quantum Chemistry, Classic Scientific Papers
1224:
348:
1590:
1643:
1629:
1482:
1139:. John Wiley & Sons, Inc. p. 25.
1549:
1134:
305:of molecules with larger, more dispersed
2035:Polyhedral skeletal electron pair theory
29:
1342:Theoretical chemistry – Lund University
1301:Angewandte Chemie International Edition
1135:Callister, William (December 5, 2000).
14:
2053:
1447:
1351:from the original on 18 September 2020
1257:LIFSHITZ, E.M.; Hamermesh, M. (1992),
1624:
1578:Molecular Theory of Gases and Liquids
919:% of the total energy of interaction
901:
361:. The perturbation is because of the
1515:
262:and highly symmetric molecules like
1593:The Theory of Intermolecular Forces
1552:Transactions of the Faraday Society
1263:Perspectives in Theoretical Physics
907:interaction energy has been given:
543:{\displaystyle E_{AB}^{\rm {disp}}}
24:
1650:
1271:10.1016/b978-0-08-036364-6.50031-4
1235:10.1016/b978-0-08-100693-1.00011-4
1203:10.1016/b978-0-12-375182-9.10021-1
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227:{\displaystyle {\frac {1}{R^{3}}}}
193:{\displaystyle {\frac {1}{R^{6}}}}
25:
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1611:Intermolecular and Surface Forces
1195:Intermolecular and Surface Forces
381:expansion of the perturbation in
270:a liquid at room temperature) or
1827:
1821:
1815:
1085:
1071:
724:is the intermolecular distance.
359:second-order perturbation theory
1599:
1584:
1569:
1543:
1487:, Singapore: World Scientific,
1441:
1399:
435:This expansion is known as the
91:
1613:(2nd ed.), Academic Press
1384:
1363:
1326:
1292:
1265:, Elsevier, pp. 329–349,
1250:
1229:, Elsevier, pp. 257–278,
1218:
1197:, Elsevier, pp. 577–616,
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1153:
1128:
401:{\displaystyle {\frac {1}{R}}}
27:Cohesive force between species
13:
1:
1335:"Intermolecular interactions"
1121:
374:is only partially satisfied.
643:{\displaystyle \alpha '_{B}}
613:{\displaystyle \alpha '_{A}}
428:is the distance between the
313:(from smallest to largest: F
7:
1064:
10:
2082:
1733:Metal–ligand multiple bond
1481:. English translations in
1371:"London Dispersion Forces"
1307:(42), Wiley: 12274–12296,
1997:
1974:
1905:
1867:
1847:
1836:
1813:
1796:
1778:
1669:
1658:
1595:, Oxford: Clarendon Press
1116:Non-covalent interactions
372:Pauli exclusion principle
349:Quantum mechanical theory
34:Interaction energy of an
1483:H. Hettema, ed. (2000),
466:{\displaystyle \alpha '}
111:that (when separated by
46:London dispersion forces
430:nuclear centers of mass
119:, typically symbolized
1450:Zeitschrift fĂĽr Physik
1408:Zeitschrift fĂĽr Physik
1313:10.1002/anie.201503476
1111:van der Waals molecule
1101:Dispersion (chemistry)
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467:
446:polarizability volumes
422:
402:
248:
228:
194:
160:
133:
42:
2061:Intermolecular forces
1514:which is reviewed in
1394:2015, 48 , 1815–1822.
879:
719:
699:
697:{\displaystyle I_{B}}
672:
670:{\displaystyle I_{A}}
645:
615:
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545:
499:ionization potentials
492:
468:
423:
403:
249:
229:
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161:
134:
108:instantaneous dipoles
33:
1723:Coordinate (dipolar)
1591:A. J. Stone (1996),
1564:10.1039/tf937330008b
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82:van der Waals forces
70:intermolecular force
66:van der Waals forces
1897:C–H···O interaction
1679:Electron deficiency
1607:Jacob Israelachvili
1530:2001PhT....54f..63H
1462:1930ZPhy...63..245L
1420:1930ZPhy...60..491E
1164:. New York: Wiley.
1106:van der Waals force
912:
858:
845:
762:
639:
609:
539:
475:ionization energies
437:multipole expansion
363:Coulomb interaction
141:wavelength of light
1882:Resonance-assisted
1470:10.1007/BF01421741
1428:10.1007/BF01341258
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902:Relative magnitude
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1999:Electron counting
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1859:London dispersion
1811:
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1788:Metal aromaticity
1580:, New York: Wiley
1538:10.1063/1.1387598
1244:978-0-08-100693-1
1212:978-0-12-375182-9
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1061:
889:molecular dipoles
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828:
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717:{\displaystyle R}
583:{\displaystyle B}
563:{\displaystyle A}
490:{\displaystyle I}
432:of the moieties.
421:{\displaystyle R}
396:
292:aqueous solutions
247:{\displaystyle R}
222:
188:
159:{\displaystyle R}
132:{\displaystyle A}
54:dispersion forces
16:(Redirected from
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2066:Chemical bonding
2040:Jemmis mno rules
1892:Dihydrogen bonds
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2013:HĂĽckel's rule
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1942:Intercalation
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1932:Metallophilic
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916:Molecule pair
915:
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393:
390:
380:
379:Taylor series
375:
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63:
59:
58:London forces
55:
51:
47:
40:
37:
32:
19:
2018:Baird's rule
1858:
1738:Charge-shift
1701:Hypervalence
1610:
1601:
1592:
1586:
1577:
1571:
1555:
1551:
1545:
1524:(6): 63–64,
1521:
1517:
1484:
1456:(3–4): 245,
1453:
1449:
1443:
1411:
1407:
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1391:
1386:
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1365:
1355:18 September
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1341:
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1300:
1294:
1284:, retrieved
1262:
1252:
1226:
1220:
1194:
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1161:
1155:
1136:
1130:
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893:
886:
503:
434:
376:
355:Fritz London
352:
300:
289:
284:condensation
260:hydrocarbons
145:
106:
98:
95:
92:Introduction
86:Fritz London
65:
61:
57:
53:
49:
45:
44:
2008:Aromaticity
1984:Heterolysis
1962:Salt bridge
1907:Noncovalent
1877:Low-barrier
1758:Aromaticity
1748:Conjugation
1728:Pi backbond
331:heteroatoms
258:), such as
256:ionic bonds
2055:Categories
1936:aurophilic
1917:Mechanical
1286:2022-08-29
1122:References
2028:spherical
1989:Homolysis
1952:Cation–pi
1927:Chalcogen
1887:Symmetric
1743:Hapticity
1503:898989103
1478:123122363
1436:125644826
848:α
835:α
767:−
764:≈
629:α
599:α
457:α
78:molecules
1957:Anion–pi
1947:Stacking
1869:Hydrogen
1780:Metallic
1671:Covalent
1663:(strong)
1609:(1992),
1558:: 8–26,
1511:9194584M
1346:Archived
1321:26262562
1180:45162154
1065:See also
856:′
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590:. Here
460:′
408:, where
368:monomers
339:chlorine
335:Fluorine
311:halogens
1922:Halogen
1768:bicyclo
1713:Agostic
1526:Bibcode
1458:Bibcode
1416:Bibcode
1376:May 24,
296:solvent
264:bromine
2023:Möbius
1851:forces
1841:(weak)
1509:
1501:
1491:
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1040:HCl-HI
473:, and
272:iodine
234:where
113:vacuum
2001:rules
1910:other
1798:Ionic
1706:3c–4e
1694:8c–2e
1689:4c–2e
1684:3c–2e
1474:S2CID
1432:S2CID
1349:(PDF)
1338:(PDF)
343:gases
280:waxes
166:like
99:(see
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1763:homo
1718:Bent
1499:OCLC
1489:ISBN
1378:2019
1357:2020
1317:PMID
1275:ISBN
1239:ISBN
1207:ISBN
1176:OCLC
1166:ISBN
1141:ISBN
1052:O-CH
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