This repository contains the computational supporting information for the manuscript 'Electronic Structure and CO2 Reactivity of Group IV/V/VI Tetraperoxometalates' submitted to The Journal of Physical Chemistry A. All parameters and structures needed to reproduce the reaction mechanism for [M(O2)4]x- + CO2 → [MO(O2)2CO3]x- + O2 are contained herein. Geometry optimizations were carried out in the Gaussian 16 Rev A.031 software package with the CAM-B3LYP functional. LAN2LZ was used for the metal center while C and O were modelled with 6-31+G*. All xyz structures contain the 298.15 K Gibbs free energy in Ha in the comment line. Calculation summaries in each directory were produced using ESIgen.2
Refer to the below table for the correct combinations of metal center, M, and complex charge, x.
| Periodic Group, Charge x = | Metal, M = |
|---|---|
| Group IV, -4 | Ti |
| " | Zr |
| " | Hf |
| Group V, -3 | V |
| " | Nb |
| " | Ta |
| Group VI, -2 | Cr |
| " | Mo |
| " | W |
The reaction mechanism sequence is
mechanism_files/
├── reaction_energies.sh # bash script with energy values and differences for DAC and decomp. rxns
├── MO4/
│ ├── CrO4.xyz # Cartesian xyz structures with Gibbs Free energy in comment line
│ ├── HfO4.xyz # Note CrO4 denotes the species [CrO_4]^2-
│ ├── MoO4.xyz
│ ├── NbO4.xyz
│ ├── TaO4.xyz
│ ├── TiO4.xyz
│ ├── VO4.xyz
│ ├── ZrO4.xyz
│ └── calculation_summaries.txt # file with
│
├── MO8/ # similarly organized directory for the tetraperoxo complexes, [M(O_2)_4]^x-
├── int1/
├── int2/
├── int3/
├── int4/
├── int4_prime/
├── ts1/
├── ts2/
├── ts3/
├── ts4_prime/
├── free_species/
│
└── MO5CO3/
├── global_min/ # globally minimized carbonatoperoxometalate product geometries
└── mechanism_end/ # locally minimized product geometries from end of mechanism
sample_inputs/
├── intermediate.com # Gaussian input files with functional+basis for the mechanism intermediates
└── transition_state.com # and transtion states
16 directories, 132 files
GitHub repository maintained by Tim J. Zuehlsdorff, tim.zuehlsdorff@oregonstate.edu