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Dicoordinate boron and phosphorus. HBCN − and HPCN − case study
Author(s) -
Liebman Joel F.,
Černušák Ivan,
Miková Andrea
Publication year - 2001
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.1316
Subject(s) - chemistry , singlet state , electron affinity (data page) , ab initio , molecular orbital , boron , ab initio quantum chemistry methods , ion , electronic correlation , molecule , antiaromaticity , ring (chemistry) , computational chemistry , electron , crystallography , ground state , atomic physics , aromaticity , physics , excited state , organic chemistry , quantum mechanics
Using ab initio calculations we predict anionic and neutral isomers of dicoordinate boron and phosphorus, HE(CN − ), HE(CN), (E=B, P). Geometries [at the MBPT(2)/aug‐cc‐PVTZ level], electron affinities, singlet–triplet (ST) splittings, and PH/BH affinities of CN − (at coupled‐clusters level) are presented. For the HBCN − chain the triplet, while for the HPCN − chain the singlet is the ground state. The rather small HEB (or HEN) bonding angles in acyclic isomers are explained on the basis of the molecular orbital (MO) picture and 1,3 interactions between hydrogen and carbon/nitrogen. Both cyanoboryl anion and cyanoboryl radical form also the ring (‐ being aromatic with two π electrons) but for the cyanophosphide the corresponding ring does not constitute a minimum on the potential energy surface. It has four π electrons and therefore is antiaromatic. Our best electron affinity estimate for HPCN is 2.44 eV, for HBCN it is 0.15 eV, while the corresponding values for the ST splittings of anions are 2.80 and −0.04 eV, respectively. Huge effects of electron correlation on calculated properties of these molecules are discussed. © 2001 John Wiley & Sons, Inc. Int J Quant Chem 84: 140–148, 2001