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Volumn 52, Issue 9, 2013, Pages 5154-5166

3c/4e δ-type long-bonding: A novel transitional motif toward the metallic delocalization limit

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EID: 84877286354     PISSN: 00201669     EISSN: None     Source Type: Journal    
DOI: 10.1021/ic4000395     Document Type: Article
Times cited : (46)

References (58)
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    • In the present work, reference to "metallic" character of 3c/4e long-bonding should not be taken to imply literal equivalence to the bulk metallic limit. Rather, the terminology identifies this semi-localized bonding motif as the characteristic alternative to conventional 2c/2e molecular covalency (and its ω-type 3c/4e extension), which plays the role of a conceptual building block in an Aufbau picture of the limiting bulk phase. NBO-based methods for condensed phases [see Dunnington, B. D.; Schmidt, J. R. J. Chem. Theory Comput. 2012, 8, 1902-1911 ] may allow further aspects of the bulk metallic limit to be investigated
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    • Note that this circumstance points to an underlying inconsistency in NBO 5.9 and preceding program versions which mandated an important notational change in the newly released NBO 6.0 version (http://nbo6.chem.wisc.edu/new6-exc.htm; Ref 35). In former NBO versions, the "*" star label is used to designate both NBOs of low occupancy ("non-Lewis" BD*, RY*) and those of out-of-phase nodal character ("antibonding" σ *, π *, etc.), which normally causes no conflict in molecular ground-state species. However, these characteristics are clearly in consistent for the high-occupancy, out-of-phase long-bond NBOs, requiring a notational change to resolve the inconsistency. In the present work (as in NBO 6.0), we employ star labels exclusively to designate out-of-phase orbital symmetry, relying on context (or labelled output section) to distinguish high-occupancy donor (Lewis) and low-occupancy (non-Lewis) acceptor NBOs. At a more practical level, it should be noted that proper characterization of δ / δ * bonding formerly required $CHOOSE and $NRTSTR keylist work-arounds [see Weinhold, F.; Landis, C. R. Discovering Chemistry with Natural Bond Orbitals; Wiley: Upper Sadde River, NJ, 2012) ], but is now handled seamlessly in NBO 6.0. NRT algorithms of NBO 6.0 have also been significantly improved, but the numerical results of the present paper are obtained with the NBO 5.9 version that is still most widely available in host electronic structure systems.
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* 이 정보는 Elsevier사의 SCOPUS DB에서 KISTI가 분석하여 추출한 것입니다.