Abstract
Molecular orbital calculations at the ab initio STO-3G, 3-21G, 4-31G, and 6-31G* bases have been made for the relative proton affinities of an extended series of substituted cyanides, XCN. It is shown that geometry optimization at the 3-21G level is adequate and that 3-21G//3-21G calculations give very similar results to those obtained at the 6-31G*//3-21G level, except for X = Cl. Gas phase proton affinities are reported for many of the XCN compounds and these values are compared with the calculated results. Agreement between theory and experiment is excellent, except for some substituents which exert large field inductive effects.
| Original language | English (US) |
|---|---|
| Pages (from-to) | 133-141 |
| Number of pages | 9 |
| Journal | Journal of Molecular Structure: THEOCHEM |
| Volume | 137 |
| Issue number | 1-2 |
| DOIs | |
| State | Published - May 1 1986 |
| Externally published | Yes |
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ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Computational Theory and Mathematics
- Atomic and Molecular Physics, and Optics
Cite this
Proton affinities of substituted cyanides. / Marriott, Stephen; Topsom, Ronald D.; Lebrilla, Carlito B.; Koppel, Ilmar; Mishima, Masaaki; Taft, Robert W.
In: Journal of Molecular Structure: THEOCHEM, Vol. 137, No. 1-2, 01.05.1986, p. 133-141.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - Proton affinities of substituted cyanides
AU - Marriott, Stephen
AU - Topsom, Ronald D.
AU - Lebrilla, Carlito B.
AU - Koppel, Ilmar
AU - Mishima, Masaaki
AU - Taft, Robert W.
PY - 1986/5/1
Y1 - 1986/5/1
N2 - Molecular orbital calculations at the ab initio STO-3G, 3-21G, 4-31G, and 6-31G* bases have been made for the relative proton affinities of an extended series of substituted cyanides, XCN. It is shown that geometry optimization at the 3-21G level is adequate and that 3-21G//3-21G calculations give very similar results to those obtained at the 6-31G*//3-21G level, except for X = Cl. Gas phase proton affinities are reported for many of the XCN compounds and these values are compared with the calculated results. Agreement between theory and experiment is excellent, except for some substituents which exert large field inductive effects.
AB - Molecular orbital calculations at the ab initio STO-3G, 3-21G, 4-31G, and 6-31G* bases have been made for the relative proton affinities of an extended series of substituted cyanides, XCN. It is shown that geometry optimization at the 3-21G level is adequate and that 3-21G//3-21G calculations give very similar results to those obtained at the 6-31G*//3-21G level, except for X = Cl. Gas phase proton affinities are reported for many of the XCN compounds and these values are compared with the calculated results. Agreement between theory and experiment is excellent, except for some substituents which exert large field inductive effects.
UR - http://www.scopus.com/inward/record.url?scp=0004512411&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=0004512411&partnerID=8YFLogxK
U2 - 10.1016/0166-1280(86)80092-6
DO - 10.1016/0166-1280(86)80092-6
M3 - Article
AN - SCOPUS:0004512411
VL - 137
SP - 133
EP - 141
JO - Computational and Theoretical Chemistry
JF - Computational and Theoretical Chemistry
SN - 2210-271X
IS - 1-2
ER -