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Issue 48, 2019
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Relatives of cyanomethylene: replacement of the divalent carbon by B, N+, Al, Si, P+, Ga, Ge, and As+

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Abstract

The lowest lying singlet and triplet states of HBCN, HCCN, HNCN+, HAlCN, HSiCN, HPCN+, HGaCN, HGeCN, and HAsCN+ were studied using the CCSDT(Q)/CBS//CCSD(T)/aug-cc-pVQZ level of theory. Periodic trends in geometries, singlet–triplet gaps, and barriers to linearity were established and analyzed. The first row increasingly favors the triplet state, with a singlet–triplet gap (ΔEST = EsingletEtriplet) of 3.5 kcal mol−1, 11.9 kcal mol−1, and 22.6 kcal mol−1, respectively, for HBCN, HCCN, and HNCN+. The second row increasing favors the singlet state, with singlet–triplet gaps of −20.4 kcal mol−1 (HAlCN), −26.6 kcal mol−1 (HSiCN), and −26.8 kcal mol−1 (HPCN+). The third row also favors the singlet state, with singlet–triplet gaps of −26.8 kcal mol−1 (HGaCN), −33.5 kcal mol−1 (HGeCN), and −33.1 kcal mol−1 (HAsCN+). The HXCN species have larger absolute singlet–triplet energy gaps compared to their parent species XH2 except for the case of X = N+. The effect of the substitution of hydrogen with a cyano group was analyzed with isodesmic bond separation analysis and NBO.

Graphical abstract: Relatives of cyanomethylene: replacement of the divalent carbon by B−, N+, Al−, Si, P+, Ga−, Ge, and As+

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Publication details

The article was received on 23 Oct 2019, accepted on 15 Nov 2019 and first published on 15 Nov 2019


Article type: Paper
DOI: 10.1039/C9CP05777C
Phys. Chem. Chem. Phys., 2019,21, 26438-26452

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    Relatives of cyanomethylene: replacement of the divalent carbon by B, N+, Al, Si, P+, Ga, Ge, and As+

    B. Z. Abbott, P. R. Hoobler and H. F. Schaefer, Phys. Chem. Chem. Phys., 2019, 21, 26438
    DOI: 10.1039/C9CP05777C

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