Exploring the Influence of (n-1)d Subvalence Correlation and of Spin-Orbit Coupling on Chalcogen Bonding
arxiv(2024)
摘要
This article presents a comprehensive computational investigation into
chalcogen bonding interactions, focusing specifically on elucidating the role
of subvalence (n-1)d and (n-1)sp correlation. The incorporation of
inner-shell (n-1)d correlation leads to a decrease in interaction energies
for chalcogen-bonded systems (at least those studied herein), contradicting the
observations regarding halogen bonding documented by Kesharwani et al. in
J. Phys. Chem. A, 2018, 122 (8), 2184-2197. The significance
of (n-1)sp subvalence correlation appears to be lower by an order of
magnitude. Notably, among the various components of interaction energies
computed at the PNO-LCCSD(T) or DF-CCSD levels, we identify the PNO-LMP2 or
DF-MP2 component of the (n-1)d correlation as predominant. Furthermore, we
delve into the impact of second-order spin-orbit coupling (SOC2) on these
interactions. Specifically, for the Te complexes, SOC2 effects rival (n-1)d
correlation in importance; for the Se complexes, SOC2 is much less important.
Generally, SOC2 stabilizes monomers more than dimers, resulting in reduced
binding of the latter. Notably, at equilibrium and stretched geometries, SOC2
and (n-1)d destabilize the complex; however, at compressed geometries, they
exhibit opposing effects, with (n-1)d becoming stabilizing.
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