The thermodynamic transition between the low-spin (LS) state and the high-spin (HS) state are usually

described within two-state models. In this case we aim for for the understanding of the entropic
contribution of certain vibrations in the spin transition comparing the molecule in isolated vacuum with
the deposited on Ir(111) surface. For this we have used the two-level Ising model in which we will add a
specific consideration of the intramolecular vibrations (Bousseksou et al.). First, we start by accounting
for the molar entropy increase with the spin transition (∆ S 0 ¿, which value is defined in its simplest
expression by eq. 1

0 g HS
∆ S =R ∙ ln (1)
g LS
where gHS and gLS are the degeneracies associated to each spin state. In this theoretical model,
extremely high values of the degeneracy ratio are needed to reach the experimental ΔS values. This
increase is usually considered to account for the density of vibrational states that is expected to be
much higher in the HS than in the LS. For simplicity we have focused in the relative entropy ratios
between isolated / deposited setup thus the specific value of vibrational HS degeneracy is not needed
for accuracy.

To include intermolecular vibrations in our two-level model, we assume that each molecule behaves as a
set of p independent harmonic oscillators with high spin frequency ( ω HS ) and low spin frequency (ω LS ).
Within this approach we fulfill the characteristics of ‘low frequencies’ where ħω ≪ k B T which makes
the ratio of the vibrational partition function independent of temperature and simplifies the final
expression. In this case, the ligand-field entropic contribution (∆ S LF ¿ , can be separated as two
components, one of the ‘spin-only degeneracy’ and the ‘vibrational contribution (eq. 2):

g HS (spin) p
ω
∆ S LF =R ∙ ln + R· ∑ LS (2)
g LS(spin) i=1 ω HS

The calculations have been performed in absence of cooperativity, assuming the average vibrational
mode is 9-fold degenerate (p=9, 3N-6 for the square-planar coordination center) and the ratio is fixed
for all the relevant vibration modes. This is a hard assumption as the rest of the atoms participating in
the vibration and all the vibrations involved should be considered explicitly. However, this naïve
approach can still be valid, as we are interested in the ratio between the isolated case and the surface
deposited molecule within the case of the first coordination center assumed to have the main
contribution responsibility.

The calculations presented in table 1 still offer values lower to the ones usually presented in the
bibliography where the ratios of (ω LS /ω HS) fall in ranges between [1.5-2.2]

Table 1:

Spin-only entropy Vibrational entropy Total Entropy (J/K·mol)

(J/K·mol) (J/K·mol)
Isolated molecule 4.2472 5.62864 9.8758
Deposited molecule 4.2472 0.5326 4.7798
Focusing in the ratio between the Isolated/deposited cases, a factor of 10.57 is found which supports
the hypothesis that the deposition hinders the free intramolecular vibrational modes that are expected
to influence the most the SCO transition. In the case of the isolated molecule in vacuum conditions, the
vibrational contribution is low but comparable to that of the spin-only entropy. However, the
confinement conditions imposed by the molecular deposition produces a minor elongation of the Fe-N
bonds for the high spin compared to what is expected in the vacuum case. This pinning produced by the
attachment to the metallic Iridium surface (with more rigid phonons that are slightly coupled with the
vibrations of the molecule) produce a removal of the vibrational entropy contribution which ends in an
absence of thermal SCO transition. (A similar uncoupled system is observed in the well-known case of
the ‘single atom magnet’, Donati et al. Science, 2016, 352, 318-321.)

(Bousseksou, A.; Constant-Machado, H.; Varret, F.; J. Phys. I France, 1995, 5, 747-760.)