Trends in M(CN) isomerism: A computational study of monocyanides of the main-group third row atoms

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Publication Date
DOI 10.1039/A901143I
Impact Factor 3.676
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Abstract

Ab initio calculations, using the G2 and G2(QCI) procedures, have been performed on the various isomers of the monocyanides of the atoms K, Ca, Ga, Ge, As, Se, and Br. In most instances, potential energy surfaces for the corresponding ions M(CN)+ have also been explored. At the levels of theory employed, π-complex minima are evident only for K(CN) and for Ca(CN)+: in almost all other instances, the global minimum is the linear cyanide geometry MCN. The barrier height to MCNMNC isomerization increases in a near-systematic fashion in going from left to right across the period; the energy difference E0(MNC)-E0(MCN) also shows a tendency to increase from M=K to M=Br. The ionization energies (IE) of both MCN and MNC increase from left to right, and in almost all cases IE(MCN)>IE(MNC). Results obtained in the present study are generally in good agreement with the (sometimes sparse) experimental record for these compounds.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
Self-citation Rate: 10.3%
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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