The First Reaction Steps of Lithium-Mediated Ammonia Synthesis: Ab Initio Simulation
Abstract
:1. Introduction
2. Results and Discussions
3. Conclusions
4. Methods
Supplementary Materials
Author Contributions
Funding
Data Availability Statement
Conflicts of Interest
Abbreviations
AIMD | Ab-Initio Molecular Dynamics |
BLYP | Becke-Lee-Yang-Parr density functional |
B3LYP | Becke-Lee-Yang-Parr hybrid density functional with three parameters |
B2PLYP | Double hybrid functional: B3LYP combined with 2nd order perturbation theory |
CCSD | Coupled-Cluster, singles, doubles |
CPMD | Car-Parrinello Molecular Dynamics |
D3BJ | Dispersion correction 3, Becke-Johnson damping |
DFT | Density functional theory |
MP2 | Moller-Plesset perturbation theory, 2nd order |
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System | Simulation | Li/N/H/O | Temp. | N-N | N-H |
---|---|---|---|---|---|
Number | [K] | Cleavage | Formation | ||
Li slab | 1 | 64/0/0/0 | 300 | no | no |
Li slab | 2 | 64/24/72/0 | 300 | no | no |
Li slab | 3 | 64/20/68/0 | 300 | yes | no |
Li slab | 4 | 64/20/64/0 | 300 | yes | no |
Li slab | 5 | 64/24/72/0 | 600 | yes | no |
Li slab | 6 | 64/20/68/0 | 600 | yes | no |
Li slab | 7 | 64/20/64/0 | 600 | yes | no |
Li slab | 8 | 64/24/72/0 | 800 | yes | no |
Li slab | 9 | 64/20/68/0 | 800 | yes | no |
Li slab | 10 | 64/20/64/0 | 800 | yes | yes |
Li slab | 11 | 64/24/72/0 | 1000 | yes | yes |
Li slab | 12 | 64/20/68/0 | 1000 | yes | no |
Li slab | 13 | 64/20/64/0 | 1000 | yes | no |
Li slab, O | 14 | 64/20/68/12 | 300 | no | no |
Li slab, O | 15 | 64/12/36/8 | 300 | no | no |
Li slab, O | 16 | 64/6/18/4 | 300 | no | no |
Li slab, O | 17 | 64/20/68/12 | 600 | no | no |
Li slab, O | 18 | 64/12/36/8 | 600 | yes | no |
Li slab, O | 19 | 64/ 6/18/4 | 600 | yes | no |
Li slab, O | 20 | 64/20/68/12 | 800 | yes | yes |
Li slab, O | 21 | 64/12/36/8 | 800 | yes | no |
Li slab, O | 22 | 64/ 6/18/4 | 800 | no | no |
Li slab, O | 23 | 64/20/68/12 | 1000 | yes | yes |
Li slab, O | 24 | 64/12/36/8 | 1000 | yes | yes |
Li slab, O | 25 | 64/6/18/4 | 1000 | yes | no |
Method | N-N | Outer Li-N | Inner Li-N |
---|---|---|---|
[Å] | [Å] | [Å] | |
BLYP | 3.04 | 1.85 | 2.02 |
BLYP/D3BJ | 3.02 | 1.84 | 2.00 |
B3LYP | 3.03 | 1.84 | 2.00 |
B3LYP/D3BJ | 3.01 | 1.83 | 1.99 |
B2PLYP | 3.04 | 1.85 | 2.01 |
B2PLYP/D3BJ | 3.03 | 1.85 | 2.01 |
MP2 | 3.11 | 1.87 | 2.06 |
CCSD | 3.06 | 1.86 | 2.02 |
Method | N-N | Outer Li-N | Central Li-N | Inner Li-N |
---|---|---|---|---|
[Å] | [Å] | [Å] | [Å] | |
BLYP | 3.96 | 1.85 | 1.91–1.94 | 2.00 |
BLYP/D3BJ | 3.89 | 1.84 | 1.91–1.93 | 1.95 |
B3LYP | 3.95 | 1.84 | 1.90–1.92 | 1.98 |
B3LYP/D3BJ | 3.89 | 1.83 | 1.90–1.91 | 1.94 |
B2PLYP | 3.98 | 1.84 | 1.92–1.93 | 1.99 |
B2PLYP/D3BJ | 3.94 | 1.84 | 1.92–1.93 | 1.97 |
MP2 | 4.04 | 1.87 | 1.94–1.95 | 2.02 |
CCSD | 4.01 | 1.85 | 1.93–1.94 | 2.01 |
Simulation | Atom | Coordination |
---|---|---|
10 | N | 6 |
10 | N | 2 |
10 | N | 6 |
10 | N | 3 |
11 | N | 6 |
11 | N | 3 |
20 | O | 3 |
20 | N | 3 |
20 | N | 5 |
23 | N | 3 |
23 | N | 4 |
23 | O | 4 |
23 | N | 3 |
23 | N | 3 |
24 | N | 4 |
24 | N | 3 |
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Maniscalco, D.; Rudolph, D.A.; Nadimi, E.; Frank, I. The First Reaction Steps of Lithium-Mediated Ammonia Synthesis: Ab Initio Simulation. Nitrogen 2022, 3, 404-413. https://doi.org/10.3390/nitrogen3030026
Maniscalco D, Rudolph DA, Nadimi E, Frank I. The First Reaction Steps of Lithium-Mediated Ammonia Synthesis: Ab Initio Simulation. Nitrogen. 2022; 3(3):404-413. https://doi.org/10.3390/nitrogen3030026
Chicago/Turabian StyleManiscalco, Dominykas, Dominik A. Rudolph, Ebrahim Nadimi, and Irmgard Frank. 2022. "The First Reaction Steps of Lithium-Mediated Ammonia Synthesis: Ab Initio Simulation" Nitrogen 3, no. 3: 404-413. https://doi.org/10.3390/nitrogen3030026