ausing the (6s6p3d1f)/4s4p3d1f contraction basis set
for Xe , the (12s12p9d3f2g) / [6s6p4d3f2g] contraction basis set for
Cu, Ag and Au ,and the aug- cc-pVTZ basis set for He, Ne and Ar.busing the aug-cc-pVQZ basis set for He, Ne and Ar and
the small-core relativistic pseudopotentials ECP28MDF for Xe.c ref 24 . dusing the large-core
relativistic pseudopotentials ECP46 MWB for Xe
3.1 Preliminary Studies:
We decided to carry out a
preliminary detailed study with various methods and basis sets on to
establish a precise context for the accuracy of our calculations on
type systems. is a particularly
appropriate molecule for benchmark calculations because it has been
experimentally and theoretically studied in detail.
Thereafter, we will use a
two-pronged evaluation strategy, including direct and indirect
evaluation methods, to assess the reliability of our theoretical results
on .
In the direct evaluation method, the reliability of our theoretical
results on AuXe42+(Sb2F11−1)2is examined by comparing our
theoretically calculated results of the spectroscopic constants, namely,
bond lengths and dissociation
energies, with previous theoretical and experimental data.
In the indirect evaluation method, we mainly focused
on
the reliability of our prediction
on the existence and stability of
based on Born–Haber cycles. This
task involves accurately estimating the lattice potential energy of .
The lattice potential energy is a dominant term in the thermodynamic
analysis of the existence and stability of ionic solids. While direct
experimental determination of the lattice potential energy is generally
impossible, we demonstrate later that
our
predictions on the existence and stability of the
ionic solid salt can be achieved by
combining our computed lattice potential energies with other known
thermodynamic functional terms, such as bond energy, sublimation
enthalpy, ionization potential, and dissociation energy
D0. Our predictions are consistent with the experimental
observation that this ionic solid salt is stable with respect to the
starting materials, and this consistency indirectly indicates that our
calculations of lattice energy are reliable.
In the indirect evaluation process, the individual ion volumes of the
cation computed in this study and used to estimate the lattice energy
are notably in good agreement with the experimental values, thus further
ensuring that our calculation results are reliable.