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A molecular orbital valence bond study of 3‐methyl sydnone and 3‐methyl pseudosydnone
Author(s) -
Shillady D. D.,
Cutler S.,
Jones L. F.,
Kier L. B.
Publication year - 1990
Publication title -
international journal of quantum chemistry
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 0.484
H-Index - 105
eISSN - 1097-461X
pISSN - 0020-7608
DOI - 10.1002/qua.560382418
Subject(s) - modern valence bond theory , valence bond theory , chemistry , molecular orbital , pi bond , antibonding molecular orbital , three center two electron bond , molecular orbital diagram , single bond , generalized valence bond , sydnone , natural bond orbital , orbital hybridisation , molecular orbital theory , sto ng basis sets , chemical bond , computational chemistry , atomic orbital , localized molecular orbitals , non bonding orbital , bond order , bond length , molecule , physics , quantum mechanics , density functional theory , electron , ring (chemistry) , alkyl , organic chemistry
A pair‐excitation‐multiconfigurational‐self‐consistent‐field ( PEMCSCF ) study with 10 configurations has been carried out on 3‐methyl‐1,2,4‐oxadiazolin‐5‐one (3‐methyl pseudosydnone) which has normal covalent bonds but is isoelectronic with 3‐methyl sydnone for which no single covalent valence bond structure can be drawn. The PEMCSCF results were found to be very similar for the two isoelectronic compounds and an attempt was made to represent the bonding of the sydnone in only two simple molecular‐orbital‐valence‐bond ( MOVB ) configurations using a Luken‐type correlating orbital. A compact minimum basis of Slater–Transform–Preuss functions fitted by six cartesian gaussian orbitals ( STP –6G) is used to express the compact representation for chemical comparison to experiment. The molecular geometry was gradient‐optimized at the single determinantal level using a 6–31G extended basis set. “Orthonormal Resonance Analysis” is given for the two dominant configurations by noting that the Boys–Reeves configuration interaction algorithm is identical to the Pauling valence bond algorithm except for use of orthogonal molecular orbitals instead of atomic hybrid orbitals. This equivalence permits use of PEMCSCF atomic charges, bond orders, and dipole moments in a slightly modified valence bond interpretation of the unusual bonding of this compound. Although forcing a larger PEMCSCF problem into a minimum basis and only two configurations raises the energy, chemical interpretation is simplified. This comparison between a mesoionic compound and an isoelectric compound with normal bonding offers new understanding of the mesoionic effect.