10.2 Wave Function Analysis 10.2.5 Localized Orbital Bonding Analysis 10.2.7 Intrinsic Atomic Orbitals

10.2.6 Oxidation State Localized Orbitals

(April 13, 2024)

Oxidation State Localized Orbitals (OSLO) is a new localization scheme focused on molecular fragments for the purposes of oxidation state assignment. ⁴⁰⁴ Gimferrer M. et al.
J. Chem. Theory Comput.
(2022), 18, pp. 309. Link The method has been developed to avoid some pitfalls encountered in the LOBA method (10.2.5) where the Pipek-Mezey orbitals can spread across many fragments without reaching the 60% threshold ⁴⁰⁵ Gimferrer M. et al.
Inorg. Chem.
(2020), 59, pp. 15410. Link . OSLO starts by looking at fragments’ centers of charge and localizing on the radial spread (in the real space) to those centers. Then, it admits orbitals to its list of orbitals if they are above a slowly increasing threshold of a criterion called the fragment orbital localization index (FOLI). To understand this criterion, one needs to know Pipek’s delocalization measure. This is defined as

d_{i}=\left[\sum_{A}(N_{A}^{i})^{2}\right]^{-1}

(10.9)

where the $N_{A}^{i}$ is the population of the $i$ th orbital on center $A$ and the summation runs over all centers. When an orbital is entirely localized on a given center, its delocalization measure is $d_{i}=1$ . If the orbital is perfectly delocalized among two centers $A$ and $B$ then $N_{A}=N_{B}=1/2$ and the delocalization measure is $d_{i}=2$ , etc. The square helps make it less sensitive to the ratio of the population to each other (insensitive to bond polarization) compared to how many are related. In fact, minimizing the sum over all occupied orbitals is precisely what leads to the Pipek-Mezey localization procedure. ⁹⁸¹ Pipek J., Mezey P. G.
J. Chem. Phys.
(1989), 90, pp. 4916. Link However, for our purposes, out of the localized orbitals generated from fragment $A$ with low delocalization measure, we are interested in those that are also highly localized on fragment $A$ . Defining the fragment orbital localization index (FOLI),

d_{i}^{A}=\left(\frac{d_{i}}{N_{A}}\right)^{1/2}\;,

(10.10)

it is easy to see $d_{i}^{A}$ tends to unity for fragment $A$ when orbital $i$ is perfectly localized on $A$ ( $d_{i}=N_{A}=1$ ), tends to 2 when the localized orbital is perfectly delocalized over two fragments ( $d_{i}=2,N_{A}=0.5$ ), and gradually increases as the orbital becomes more delocalized as well as less centered on fragment $A$ . Thus, among the redundant set of $Mn_{occ}$ localized orbitals, one selects all orbitals above the smallest FOLI by a threshold (0.01 by default) and assigns each orbital to the originator fragment. The orbitals are then symmetrically orthogonalized and projected out from the remaining space of (unassigned) occupied space. In case a set of orbitals is redundant due to symmetry in the system or simple covalency, then the orbitals are split over all contributing fragments (originators). After the iterative process, each molecular fragment has an associated set of localized orbitals derived from the simplest orbital spread criterion, which in turn determines the fragment’s formal charge or oxidation state in a natural manner.

The new method expects fragments. Otherwise, it localizes on atomic centers instead. Although this method was developed for oxidation state, it produces a set of localized orbitals on fragments or atoms that can be used like any other localization method.

OSLO

OSLO
       Triggers OSLO procedure after a converged SCF
TYPE:
       INTEGER
DEFAULT:
       0
OPTIONS:
       0 Don’t perform OSLO 1 Perform the OSLO procedure
RECOMMENDATION:
       None

More precise control of OSLO goes under the $loco input section, with keywords that are introduced below. See the example for reference.

OSLO_POPANALTYPE
       Specifies which population analysis is used for OSLOs.
INPUT SECTION: $loco
TYPE:
       INTEGER
DEFAULT:
       2
OPTIONS:
       0 Mulliken 1 Lowdin 2 IAOs
RECOMMENDATION:
       Use IAOs since they are insenstive to the basis set. When using IAOs, use AUTOSAD = TRUE in the $loco input section to use the new AUTOSAD-IAO algorithm, which uses AUTOSAD atomic densities instead of some minimal basis.

OSLO_THRESH
       Specifies the threshold for FOLI when adding new orbitals for each iteration.
INPUT SECTION: $loco
TYPE:
       INTEGER
DEFAULT:
       0
OPTIONS:
       0 Use the default, 0.01 $c$ Use threshold of $c$ /1000
RECOMMENDATION:
       Use the default

OSLO_BRANCHING
       Specifies which iteration with too much overlap between its orbitals and next sets orbitals to choose the next set. The input here can be $abcdf\ldots$ , which is a binary string for which iteration (only consider those with warning prints) to branch in, e.g., 010011, means to branch in iterations 2, 5, and 6.
INPUT SECTION: $loco
TYPE:
       INTEGER
DEFAULT:
       0
OPTIONS:
       $abcd\ldots$ , for each digit: 0 Follow the default behavior 1 Favor the next set of orbitals over the current set
RECOMMENDATION:
       Use the default, and only worry about this if the system involves multiple Lewis structures

Example 10.2 An OSLO job to analyze the oxidation state (or formal charges) of the water molecule, $\rm H_{2}O$

$molecule
0 1
--
0 2
H  0.7493679  0.000000   0.44243272
--
0 3
O  0.0000000  0.000000  -0.16535063
--
0 2
H -0.7493679  0.000000   0.44243272
$end

$rem
jobtype       sp
method        wB97X-V
basis         def2-TZVP
ecp           def2-ecp
mem_total     64000
mem_static    4000
point_group_symmetry False
integral_symmetry false
scf_algorithm DIIS
scf_convergence 9
thresh        14
max_scf_cycles 1000
oslo          6
$end

$loco
autosad 1
ibo_mem 500
print_level 0
oslo_popanaltype 2
$end

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10.2.6 Oxidation State Localized Orbitals