The use of the MNDO SCF MO method in UPS band-assignments for unsaturated hydrocarbons and fluorocarbons

Chiang, Hui-Jean; Worley, S. D.

doi:10.1016/0368-2048(80)85042-0

Cited by 17 publications

(1 citation statement)

References 53 publications

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“…The situation became even more complicated when it was found that the MNDO model gave results in harmony with the original interpretation. 136 The origin of these discrepancies is the extreme sensitivity of through-space and through-bond interaction with respect to small changes in geometry.134 Thus, it has finally been observed, using the HAM/3 model with MM1/MM2 geometries, that there is-dependent on the chosen geometry-a nonnegligible, significant mixing of 7r_(bu) and <r(bu) orbitals in 8 and of 7r_(b2) and <r(b2) levels in 9.137 Recently, ab initio Cl calculations, using a partially MINDO/2-optimized structure, gave results in accordance with the simple HAM/3 model.137®…”

Section: Cubane (1)mentioning

confidence: 99%

Consequences of strain in (CH)8 hydrocarbons

Hassenrueck¹,

Martin²,

Walsh³

1989

Chem. Rev.

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Section: Cubane (1)mentioning

confidence: 99%

Consequences of strain in (CH)8 hydrocarbons

Hassenrueck¹,

Martin²,

Walsh³

1989

Chem. Rev.

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Proximitätseffekte in der Organischen Chemie — Die photoelektronenspektroskopische Untersuchung nichtbindender und transanularer Wechselwirkungen

Martin

Mayer

1983

Angewandte Chemie

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Klassische Strukturformeln vermitteln hiiufig die Vorstellung, einzig und a h i n jene Beziehungen zwischen den Atomen seien von Bedeutung, welche fur den Zusammenhalt des Molekiils sorgen und durch Bindungsstriche wiedergegeben werden. Viele Wechselwirkungen zwischen Atomen oder Atomgruppen werden jedoch durch diese Schreibweise nicht erfaBt. Ihre Anwesenheit hat dennoch mitunter wichtige Konsequenzen fiir Grundzustandsenergien (cis-Difluorethylen ist stabiler als trans-Difluorethylen), Konformationen (syn-Methylvinylether ist stabiler als die anti-Form), Reaktiuituten (ein endo-standiger Cyclopropanring in 7anti-Norbornylderivaten beschleunigt die Solvolyse um den Faktor IOl4), UV-Spektren (die n-Systeme von Acridin und Purindurch eine viergliedrige Kette verbundenergeben beim ,,Ubereinanderlegen" Hypochromie), CD-Spektren (der inhiirent symmetrische, dissymmetrisch gestarte Chromophor von 2-Deuterionorbornadien IiiBt drei Ubergiinge im nahen UV erkennen) und ESR-Spektren (die Fernkopplung mit H-4 im Briickenkopf-Radikal Bicyclo[2.l.l]hex-l-yl betriigt 22.5 G). An den meisten intramolekularen Effekten dieser Art sind Orbitalwechselwirkungen beteiligt ; die Photoefektronenspektroskopie hat sich wie erwartet als aussagekraftige und wertvolle Erganzung der anderen Methoden erwiesen.

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Proximity Effects in Organic Chemistry—The Photoelectron Spectroscopic Investigation of Non‐Bonding and Transannular Interactions

Martin

Mayer

1983

Angew. Chem. Int. Ed. Engl.

160

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Classical structural formulas often convey the impression onb those relationships between the atoms are of importance which hold a molecule together as symbolized by the chemical bonds. However, many interactions between atoms or groups of atoms are not adequately denoted in this manner. Nevertheless, their existence can have important consequences for ground state energies (cis-difluoroethylene is more stable than trans-difluoroethylene), conformations (the syn form of methyl vinyl ether is more stable than the anti form), reactivities (an endo cyclopropane ring in 7-anti-norbornyl derivatives accelerates solvolysis by a factor of UV spectra ("superposition" of the n-systems of acridine and purine-bonded through a four-membered chain-results in hypochromism), CD spectra (the inherently symmetrical but dissymmetrically perturbed chromophore of 2-deuterionorbornadiene allows the observation of three transitions in the near UV), and ESR spectra (the long-range coupling with H-4 in the bridgehead bicyclo[2.l.l]hex-l-yl radical equals 22.5 G). Since orbital interactions are involved in most intramolecular effects of this kind, photoelectron spectroscopy has proven an informative and valuable extension to other methods.

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The use of the MNDO SCF MO method in UPS band-assignments for unsaturated hydrocarbons and fluorocarbons

Cited by 17 publications

References 53 publications

Consequences of strain in (CH)8 hydrocarbons

Consequences of strain in (CH)8 hydrocarbons

Proximitätseffekte in der Organischen Chemie — Die photoelektronenspektroskopische Untersuchung nichtbindender und transanularer Wechselwirkungen

Proximity Effects in Organic Chemistry—The Photoelectron Spectroscopic Investigation of Non‐Bonding and Transannular Interactions

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