“Chirgwin–Coulson weights”的意思、由来-开放百科全书

In modern valence bond (VB) theory calculations, Chirgwin–Coulson weights (also called Mulliken weights) are the relative weights of a set of possible VB structures of a molecule. Related methods of finding the relative weights of valence bond structures are the Löwdin^[1] and the inverse weights.^[2]

Background

For a wave function

where

are a linearly independent, orthogonal set of basis orbitals, the weight of a constituent orbital

would be

since the overlap integral,

, between two wave functions

would be 1 for

and 0 for

. In valence bond theory, however, the generated structures are not necessarily orthogonal with each other, and often times have substantial overlap between the two structures. As such, when considering non-orthogonal constituent orbitals (i.e. orbitals with non-zero overlap) the non-diagonal terms in the overlap matrix would be non-zero, and must be included in determining the weight of a constituent orbital. A method of computing the weight of a constituent orbital,

, proposed by Chirgwin and Coulson would be:^[2]

Application of the Chirgwin-Coulson formula to a molecular orbital yields the Mulliken population of the molecular orbital.^[3]

Rigorous Formulation

Determination of VB Structures

Rumer's Method

A method of creating a linearly independent, complete set of valence bond structures for a molecule was proposed by Yuri Rumer. For a system with n electrons and n orbitals, Rumer's method involves arranging the orbitals in a circle and connecting the orbitals together with lines that do not intersect one another.^[4] Covalent, or uncharged, structures can be created by connecting all of the orbitals with one another. Ionic, or charged, structures for a given atom can be determined by assigning a charge to a molecule, and then following Rumer's method. For the case of butadiene, the 20 possible Rumer structures are shown, where 1 and 2 are the covalent structures, 3-14 are the monoionic structures, and 15-20 are the diionic structures. The resulting VB structures can be represented by a linear combination of determinants

, where a letter without an over-line indicates an electron with

spin, while a letter with over-line indicates an electron with

spin. The VB structure for 1, for example would be a linear combination of the determinants

, and

. For a monoanionic species, the VB structure for 11 would be a linear combination of

and

, namely:

Matrix Representation of VB Structures

An arbitrary VB structure

containing

electrons, represented by the electron indices

, and

orbitals, represented by

, can be represented by the following Slater determinant:

Where

and

represent an

spin on the

electron, respectively. For the case of a two electron system with orbitals

and

, the VB structure,

, can be represented:

Definition of Chirgwin Coulson Weights

Given a wave function

where

is a complete, linearly independent set of VB structures and

is the coefficient of each structure, the Chirgwin-Coulson weight

of a VB structure

can be computed in the following manner:^[2]

Other methods of computing weights of VB structure include Löwdin weights, where

,^[1] and inverse weights, where

with

being a normalization factor defined by

.^[6] The use of Löwdin and inverse weights is appropriate when the Chirgwin–Coulson weights either exceed 1 or are negative.^[6]

Half Determinant Decomposition of Molecular Orbitals

Given a set of molecular orbitals,

, for a molecule, consider the determinant of a given orbital population, represented by

. The determinant can be written as the following Slater determinant:

Computing the determinant explicitly by multiplying this expression can be a computationally difficult task, given that each molecular orbital is composed of a combination of atomic orbitals. On the other hand, because the determinant of a product of matrices is equal to the product of determinants, the determinant can be regrouped to half-determinants, one of which contains only electrons with

spin and the only with electrons of

spin, that is:

where

and

.^[5]^[7]^[13]

Note that any given molecular orbital

can be written as a linear combination of atomic orbitals

, that is for each

, there exist

such that

. As such, the half determinant

can be further decomposed into the half determinants for an ordering of atomic orbitals

corresponding to a VB structure

. As such, the molecular orbital

can be represented as a combination of the half determinants of the atomic orbitals,

. The coefficient

can be determined by evaluating the following matrix:^[5]^[7]^[13]

The same method can be used to evaluate the half determinant for the

electrons,

. As such, the determinant

can be expressed as

, where

index across all possible VB structures.^[5]^[7]^[13]

Sample Computations for Simple Molecules

Computations for the Hydrogen Molecule

The hydrogen molecule can be considered to be a linear combination of two H

orbitals, indicated as

and

. The possible VB structures for H_2 are the two covalent structures,

and

indicated as 1 and 2 respectively, as well as the ionic structures

and

indicated as 3 and 4 respectively, shown below.

Because structures 1 and 2 both represent covalent bonding in the hydrogen molecule and exchanging the electrons of structure 1 yields structure 2, the two covalent structures can be combined into one wave function. As such, the Heitler-London model for bonding in H_2,

, can be used in place of the VB structures

and

:^[8]

Where the negative sign arises from the antisymmetry of electron exchange. As such, the wave function for the H_2 molecule,

, can be considered to be a linear combination of the Heitler-London structure and the two ionic valence bond structures.

The overlap matrix between the atomic orbitals between the three valence bond configurations

, and

is given in the output for valence bond calculations. A sample output is given below:^[5]

Finding the eigenvectors of the matrix

, where

is the hamiltonian and

is energy due to orbital overlap, yields the VB-vector

, which satisfies:^[9]

Solving for the VB-vector

using density functional theory yields the coefficients

and

. Thus, the Coulson-Chrigwin weights can be computed:^[5]

To check for consistency, the inverse weights can be computed by first determining the inverse of the overlap matrix:

Informally, the computed weights indicate that the wave function for the H_2 molecule has a minor contribution from an ionic species not predicted from a strictly MO model for bonding.

Computations for Ozone

Determining the relative weights of each resonance structure of ozone requires, first, the determination of the possible VB structures for O_3. Considering only the

orbitals of oxygen, and labeling the

orbital on the

oxygen

, O_3has 6 possible VB structures by Rumer's method. Assuming no atomic orbital overlap, the

structure can be represented by the determinants

:^[5]

O_3has the following three molecular orbitals, one where all of the oxygen

orbitals are in phase, one where there is a node on the central oxygen, and one where all of the oxygen

orbitals are out of phase, shown below:

The wave functions for each of the molecular orbitals

can be written as a linear combination of each of the oxygen

orbitals as follows:^[5]

Where

indicates the coefficient of

in a molecular orbital

. Consider, the VB contributions for the ground state of O_3,

. Using the methods of half determinants, the half determinants for the ground state are:

By the method of half determinant expansion, the coefficient,

, for a structure

is:

The overlap between two VB structures represented by the product of two VB determinants

can be evaluated by finding the product of the overlap between the two half determinants, that is:

The weights of the standard Lewis structures for O_3 would be

and

. The weights can be found by first computing the Chirgwin–Coulson weights for their constituent determinants:

The weights for the standard lewis structures would be the sum of the weights of the constituent determinants. As such:^[2]

This compares well with reported Chirgwin–Coulson weights of 0.226 for the standard Lewis structure of ozone in the ground state.^[10]

This also compares favorably with reported Chirgwin–Coulson weights of 0.213 for the diradical state of ozone in the ground state.^[10]

Applications to Main Group Compounds

Borazine

Borazine, (chemical formula B_3N_3H_6) is a cyclic, planar compound that is isoelectronic with benzene. Given the lone pair in the nitrogen p orbital out of the plane and the empty p orbital of boron, the following resonance structure is possible:

However, VB calculations using a double‐zeta D95 basis set indicate that the predominant resonance structures are the structure with all three lone pairs on the nitrogen (labeled 1 below) and the six resonance structures with one double bond between boron and nitrogen (labeled 2 below). The relative weights of the two structures are 0.17 and 0.08 respectively.^[11]^[12]

By contrast, the dominant resonance structures of benzene are the two Kekule structures, with weight 0.15, and 12 monozwitterionic structures with weight 0.03. The data, together, indicate that, despite the similarity in appearance and structure, the electrons on borazine are less delocalized than those on benzene.^[11]

S₂N₂

Disulfur dinitride is a square planar compound that contains a 6 electron conjugated

system. The primary diradical resonance structures (1 and 2) and a secondary zwitterionic structure (3) are shown below:

Valence bond calculations using the Dunning's D95 full double-zeta basis set indicate that the dominant resonance structure is the singlet diradical with a long nitrogen-nitrogen bond (structure 1), with Chirgwin-Coulson weight 0.47. This value is substantially higher than the weight for the singlet diradical centered on the sulfurs (structure 2), which has a Chirgwin-Coulson weight of 0.06.^[13] This result corresponds nicely with the general rules regarding Lewis structures, namely that formal charges ought to be minimized, and contrasts with earlier computational results indicating that 1 is the dominant structure.^[14]

References

1. ^¹{{Cite journal|last=Löwdin|first=Per‐Olov|date=March 1953|title=On the Molecular‐Orbital Theory of Conjugated Organic Compounds with Application to the Perturbed Benzene Ring |journal=The Journal of Chemical Physics|volume=21|issue=3|pages=496–515|doi=10.1063/1.1698934|issn=0021-9606|bibcode=1953JChPh..21..496L}}
2. ^¹²{{Cite journal|last=Chirgwin|first=B. H.|last2=Coulson|first2=C. A.|date=22 March 1950|title=The Electronic Structure of Conjugated Systems. VI |journal=Proceedings of the Royal Society A: Mathematical, Physical and Engineering Sciences|volume=201|issue=1065|pages=196–209|doi=10.1098/rspa.1950.0053|issn=1364-5021|bibcode=1950RSPSA.201..196C}}
3. ^{{Cite journal|last=Mulliken|first=R. S.|date=October 1955 |title=Electronic Population Analysis on LCAO–MO Molecular Wave Functions. I |journal=The Journal of Chemical Physics|volume=23|issue=10|pages=1833–1840|doi=10.1063/1.1740588|issn=0021-9606|bibcode=1955JChPh..23.1833M}}
4. ^{{Cite journal|last=Rumer|first=Georg|date=1932|title=Zur Theorie der Spinvalenz |url=https://gdz.sub.uni-goettingen.de/id/PPN252457811_1932?tify={%22pages%22:[341],%22panX%22:0.569,%22panY%22:0.825,%22view%22:%22info%22,%22zoom%22:0.52}|journal=Gottinger Nachr.|volume=|pages=337}}
5. ^¹²³⁴⁵⁶⁷⁸{{Cite book|doi=10.1002/9780470192597 |title=A Chemist's Guide to Valence Bond Theory|last=Shaik|first=Sason|last2=Hiberty|first2=Philippe C.|date=2007-11-16|publisher=John Wiley & Sons, Inc.|isbn=9780470192597|location=Hoboken, NJ, USA}}
6. ^¹²{{Cite journal|last=Gallup|first=G.A.|last2=Norbeck|first2=J.M.|date=September 1973 |title=Population analyses of valence-bond wavefunctions and BeH2 |journal=Chemical Physics Letters|volume=21|issue=3|pages=495–500|doi=10.1016/0009-2614(73)80292-1|issn=0009-2614|bibcode=1973CPL....21..495G}}
7. ^¹²{{Cite book|last=Shaik|first=Sason|chapter=Valence Bond Theory, Its History, Fundamentals, and Applications: A Primer|date=2004-08-17 |doi=10.1002/0471678856.ch1|title=Reviews in Computational Chemistry|pages=1–100|publisher=John Wiley & Sons, Inc.|isbn=9780471445258 |last2=Hiberty|first2=Philippe C.}}
8. ^{{Cite journal|last=Heitler|first=W.|last2=London|first2=F.|date=June 1927 |title=Wechselwirkung neutraler Atome und homöopolare Bindung nach der Quantenmechanik|journal=Zeitschrift für Physik|volume=44|issue=6–7|pages=455–472|doi=10.1007/bf01397394|issn=1434-6001|bibcode=1927ZPhy...44..455H}}
9. ^J. Verbeek, J. H. Langenberg, C. P. Byrman, F. Dijkstra, J. H. van Lenthe, TURTLE: An Ab Initio VB/VBSCF Program (1998–2000)
10. ^¹²³⁴{{Cite journal|last=Hiberty|first=P. C.|last2=Leforestier|first2=C.|date=March 1978|title=Expansion of molecular orbital wave functions into valence bond wave functions. A simplified procedure |journal=Journal of the American Chemical Society|volume=100|issue=7|pages=2012–2017|doi=10.1021/ja00475a007|issn=0002-7863}}
11. ^¹{{Cite journal|last=Benker|first=Daniel|last2=Klapötke|first2=Thomas M.|last3=Kuhn|first3=Gerhard|last4=Li|first4=Jiabo|last5=Miller|first5=Christian|date=2005|title=An ab initio valence bond (VB) calculation of the π delocalization energy in borazine, B3N3H6|journal=Heteroatom Chemistry|volume=16|issue=5|pages=311–315|doi=10.1002/hc.20095|issn=1042-7163}}
12. ^Engelberts, Jeroen Johan. “Analysis Of Chemical Bonding Using Ab Initio Valence Bond Theory.” Utrecht University, 2017.

13. ^{{Cite journal|last=Klapoetke|first=Thomas M.|last2=Li|first2=Jiabo|last3=Harcourt|first3=Richard D.|date=2004-10-12|title=Ab initio Double-ζ (D95) Valence Bond Calculations for the Ground States of S2N2 and S42+ |journal=ChemInform|volume=35|issue=41|doi=10.1002/chin.200441002|issn=0931-7597}}
14. ^{{Cite journal|last=Gerratt|first=J.|last2=McNicholas|first2=S. J.|last3=Karadakov|first3=P. B. |last4=Sironi|first4=M.|last5=Raimondi|first5=M.|last6=Cooper|first6=D. L.|date=January 1996|title=The Extraordinary Electronic Structure of N2S2 |journal=Journal of the American Chemical Society|volume=118|issue=27|pages=6472–6476|doi=10.1021/ja953994f|issn=0002-7863}}