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The nature of the X\uf8ffE bonding has been analyzed with charge\u2010 and energy\u2010partitioning methods. The calculations show that the linear isomers of the nitrogen systems <jats:italic><jats:bold>lin<\/jats:bold><\/jats:italic><jats:bold>\u2010HEN<\/jats:bold> and <jats:italic><jats:bold>lin<\/jats:bold><\/jats:italic><jats:bold>\u2010HNE<\/jats:bold> are minima on the singlet PES. The carbon compound <jats:italic><jats:bold>lin<\/jats:bold><\/jats:italic><jats:bold>\u2010HCN<\/jats:bold> (HCN=hydrogen cyanide) is 14.9\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup> lower in energy than <jats:italic><jats:bold>lin<\/jats:bold><\/jats:italic><jats:bold>\u2010HNC<\/jats:bold> but the heavier group\u200514 homologues <jats:italic><jats:bold>lin<\/jats:bold><\/jats:italic><jats:bold>\u2010HEN<\/jats:bold> (E=Si\u2013Pb) are between 64.8 and 71.5\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup> less stable than the <jats:italic><jats:bold>lin<\/jats:bold><\/jats:italic><jats:bold>\u2010HNE<\/jats:bold> isomers. The phosphorous system (H, P, E) exhibits significant differences concerning the geometry and stability of the equilibrium structures compared with the nitrogen system. The linear form <jats:italic><jats:bold>lin<\/jats:bold><\/jats:italic><jats:bold>\u2010HEP<\/jats:bold> of the former system is much more stable than <jats:italic><jats:bold>lin<\/jats:bold><\/jats:italic><jats:bold>\u2010HPE<\/jats:bold>. The molecule <jats:italic><jats:bold>lin<\/jats:bold><\/jats:italic><jats:bold>\u2010HCP<\/jats:bold> is the only minimum on the singlet PES. It is 78.5\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup> lower in energy than <jats:italic><jats:bold>lin<\/jats:bold><\/jats:italic><jats:bold>\u2010HPC<\/jats:bold>, which is a second\u2010order saddle point. The heavier homologues <jats:italic><jats:bold>lin<\/jats:bold><\/jats:italic><jats:bold>\u2010HPE<\/jats:bold>, in which E=Si\u2013Pb, are also second\u2010order saddle points, whereas the <jats:italic><jats:bold>bent<\/jats:bold><\/jats:italic><jats:bold>\u2010HPE<\/jats:bold> structures are the global minima on the PES. They are between 10.3 (E=Si) and 36.5\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup> (E=Pb) lower in energy than <jats:italic><jats:bold>lin<\/jats:bold><\/jats:italic><jats:bold>\u2010HEP<\/jats:bold>. The <jats:italic><jats:bold>bent<\/jats:bold><\/jats:italic><jats:bold>\u2010HPE<\/jats:bold> structures possess rather acute bending angles H\u2010P\u2010E between 60.1 (E=Si) and 79.7\u00b0 (E=Pb). The energy differences between the heavier group\u200515 isomers <jats:italic><jats:bold>lin<\/jats:bold><\/jats:italic><jats:bold>\u2010HEX<\/jats:bold> (X=P\u2013Bi) and the bent structures <jats:italic><jats:bold>bent<\/jats:bold><\/jats:italic><jats:bold>\u2010HXE<\/jats:bold> become continuously smaller. The silicon species <jats:italic><jats:bold>lin<\/jats:bold><\/jats:italic><jats:bold>\u2010HSiBi<\/jats:bold> is even 3.1\u2005kcal\u2009mol<jats:sup>\u22121<\/jats:sup> lower in energy than <jats:italic><jats:bold>bent<\/jats:bold><\/jats:italic><jats:bold>\u2010HBiSi<\/jats:bold>. The bending angle H\u2010X\u2010E becomes more acute when X becomes heavier. The drastic energy differences between the isomers of the system (H, X, E) are explained with three factors that determine the relative stabilities of the energy minima: 1)\u2005The different bond strength between the hydrogen bonds H\uf8ffX and H\uf8ffE. 2)\u2005The electronic excitation energy of the fragment HE from the X <jats:sup>2<\/jats:sup>\u03a0 ground state to the <jats:sup>4<\/jats:sup>\u03a3<jats:sup>\u2212<\/jats:sup> excited state, which is required to establish a E\u2261X triple bond in the molecules <jats:italic><jats:bold>lin<\/jats:bold><\/jats:italic><jats:bold>\u2010HEX<\/jats:bold>. 3)\u2005The strength of the intrinsic X\uf8ffE interactions in the molecules. The trends of the geometries and relative energies of the linear, bent, and cyclic isomers are explained with an energy\u2010decomposition analysis that provides deep insight into the nature of the bonding situation.<\/jats:p>","DOI":"10.1002\/asia.201200022","type":"journal-article","created":{"date-parts":[[2012,4,13]],"date-time":"2012-04-13T16:28:48Z","timestamp":1334334528000},"page":"1296-1311","source":"Crossref","is-referenced-by-count":22,"title":["Are They Linear, Bent, or Cyclic? 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AIM calculations with the smaller basis set SVP do not give a H\uf8ffSi bond path."},{"key":"e_1_2_6_70_2","unstructured":"It should be noted however that stronger attractions do not necessarily yield a shortening of a bond. The results for the linear and bent formslin\u2010HXEandbent\u2010HXEshow that the X\uf8ffE bonds in the latter species are longer but much stronger than in the former isomers. Further examples and an explanation for the finding have been given in:"},{"key":"e_1_2_6_71_2","doi-asserted-by":"publisher","DOI":"10.1021\/om00011a058"},{"key":"e_1_2_6_72_2","doi-asserted-by":"publisher","DOI":"10.1016\/S0022-328X(96)06512-6"},{"key":"e_1_2_6_73_2","doi-asserted-by":"publisher","DOI":"10.1021\/ja9716463"},{"key":"e_1_2_6_74_2","doi-asserted-by":"publisher","DOI":"10.1021\/om020311d"},{"key":"e_1_2_6_75_2","doi-asserted-by":"publisher","DOI":"10.1201\/9781420007282"},{"key":"e_1_2_6_76_2","unstructured":"\u00a0"},{"key":"e_1_2_6_77_2","doi-asserted-by":"publisher","DOI":"10.1007\/s00214-003-0535-2"},{"key":"e_1_2_6_78_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200400525"},{"key":"e_1_2_6_79_2","doi-asserted-by":"publisher","DOI":"10.1002\/chem.200600564"},{"key":"e_1_2_6_80_2","doi-asserted-by":"publisher","DOI":"10.1002\/ange.19840960405"},{"key":"e_1_2_6_80_3","doi-asserted-by":"publisher","DOI":"10.1002\/anie.198402721"},{"key":"e_1_2_6_81_2","unstructured":"We take the energy difference between the two isomers as a measure of the stability. 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