Bonding and singlet–triplet gap of silicon trimer: Effects of protonation and attachment of alkali metal cations

ISSN： 0192-8651

Source： JOURNAL OF COMPUTATIONAL CHEMISTRY, Vol.36, Iss.11, 2015-04, pp. : 805-815

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Abstract

We revisit the singlet–triplet energy gap (ΔEST) of silicon trimer and evaluate the gaps of its derivatives by attachment of a cation (H+, Li+, Na+, and K+) using the wavefunction‐based methods including the composite G4, coupled‐cluster theory CCSD(T)/CBS, CCSDT and CCSDTQ, and CASSCF/CASPT2 (for Si3) computations. Both 1A1 and 3A2' states of Si3 are determined to be degenerate. An intersystem crossing between both states appears to be possible at a point having an apex bond angle of around α = 68 ± 2° which is 16 ± 4 kJ/mol above the ground state. The proton, Li+ and Na+ cations tend to favor the low‐spin state, whereas the K+ cation favors the high‐spin state. However, they do not modify significantly the ΔEST. The proton affinity of silicon trimer is determined as PA(Si3) = 830 ± 4 kJ/mol at 298 K. The metal cation affinities are also predicted to be LiCA(Si3) = 108 ± 8 kJ/mol, NaCA(Si3) = 79 ± 8 kJ/mol and KCA(Si3) = 44 ± 8 kJ/mol. The chemical bonding is probed using the electron localization function, and ring current analyses show that the singlet three‐membered ring Si3 is, at most, nonaromatic. Attachment of the proton and Li+ cation renders it anti‐aromatic. © 2015 Wiley Periodicals, Inc.