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The Photochemistry of 1,3‐Butadiene Rationalized by Means of Theoretical Resonance Structures and Their Weights
Author(s) -
Bachler Vinzenz,
Schaffner Kurt
Publication year - 2000
Publication title -
chemistry – a european journal
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 1.687
H-Index - 242
eISSN - 1521-3765
pISSN - 0947-6539
DOI - 10.1002/(sici)1521-3765(20000317)6:6<959::aid-chem959>3.0.co;2-d
Subject(s) - singlet state , resonance (particle physics) , excited state , chemistry , ground state , wave function , complete active space , molecule , atomic physics , computational chemistry , molecular orbital , physics , organic chemistry
A complete active‐space self‐consistent‐field wave function for the π‐electron part of s‐ trans ‐1,3‐butadiene has been expanded into a set of localized bonding schemes and their weights. These bonding schemes are close to the resonance structures used in organic chemistry. The expansion technique has been applied to both the electronic ground state and the electronically first‐excited singlet and triplet π,π* states. The manifolds of large‐weight bonding schemes represent approximate resonance hybrids for the ground and the singlet and triplet π,π* states of s‐ trans‐ 1,3‐butadiene. These resonance hybrids, obtained by theory alone, permit a qualitative rationalization of a significant part of the known singlet and triplet photochemistry.