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Structure of Molecular PNO, Matrix Isolation and ab initio Calculations
Author(s) -
Ahlrichs Reinhart,
Schunck Stephan,
Schnöckel Hansgeorg
Publication year - 1988
Publication title -
angewandte chemie international edition in english
Language(s) - English
Resource type - Journals
SCImago Journal Rank - 5.831
H-Index - 550
eISSN - 1521-3773
pISSN - 0570-0833
DOI - 10.1002/anie.198804211
Subject(s) - matrix isolation , ab initio , photodissociation , physics , intuition , matrix (chemical analysis) , ab initio quantum chemistry methods , atomic physics , crystallography , chemistry , argon , molecule , quantum mechanics , philosophy , photochemistry , epistemology , chromatography
Molecular PNO is formed upon photolysis of PN and O 3 in an argon matrix. From the IR spectrum its structure can be formulated as \documentclass{article}\usepackage{amssymb}\pagestyle{empty}\begin{document}${\rm P} \begin{array}{c}\hbox{---}\\[-11pt]\hbox{---}\\[-10pt]\raise1pt\hbox{---}\\\end{array}\mathop {\rm N}\limits^\oplus \raise1pt\hbox{---}\mathop {\rm O}\limits^\ominus$\end{document} , since a band at ṽ = 1755 cm −1 can only be assigned to a NO vibration. This structure contradicts chemical intuition, according to which the isomer NPO should be more stable, but is in agreement with the results of quantum chemical calculations, which show that PNO is 22 kJ mol −1 more stable than NPO.