Iron-based magnetic superhalogens with pseudohalogens as
ligands: An unbiased structure search
Li Ping Ding1, Peng Shao2,*, Cheng Lu3,*, Fang Hui Zhang1, Li Ya Wang3, *
Department of Optoelectronic Science & Technology, College of Elecrical & Information
1
Engineering, Shanxi University of Science & Technology, Xian, 710021, China.
Department of Physics, Shaanxi University of Science & Technology, Xi’an, 710021, China.
2
Department of Physics, Nanyang Normal University, Nanyang, 473061, China.
3
*Correspondence author. E-mail: [email protected] (Peng Shao), [email protected] (Cheng Lu),
[email protected] (Li Ya Wang).
Neutral
Isomer
distance
(Å)
Fe(BO2)4
1.649
Fe(CN)4
1.954
Fe(NO2)4
1.834
Fe(NO3)4
2.060
Fe(OH)4
1.787
Fe(CH3)4
2.036
Fe(NH2)4
1.847
Fe(BH4)4
1.874
Fe(Li2H3)4
1.669
Anion
frequency (cm-1)
2097, 2080,1397,
1365, 1344, 1271
2456, 2330, 2227,
2130, 981, 573
1750, 1724, 1719,
1350, 1333, 1221
1695, 1673, 1672,
1198, 1186, 1183
3776, 3772, 3772,
3771, 845, 835
3132, 3128, 3127,
3066, 3065, 3041
3645, 3644, 3630,
3629, 3536, 3532
4393, 2646, 2641,
2622, 2618, 2557
4348, 1495, 1399,
1383, 1337, 1282
Isomer
distance
(Å)
Fe(BO2)4¯
1.878
Fe(CN)4¯
2.021
Fe(NO2)4¯
1.905
Fe(NO3)4¯
2.097
Fe(OH)4¯
1.899
Fe(CH3)4¯
2.114
Fe(NH2)4¯
1.972
Fe(BH4)4¯
1.859
Fe(Li2H3)4¯
1.756
frequency (cm-1)
2061, 2035, 2015,
1334, 1258, 1163
2210, 2209, 2209,
2208, 428, 427
1631, 1612, 1611,
1611, 954, 918
1610, 1585, 1578,
1578, 1283, 1275
3807, 3807, 3806,
3806, 679, 678
3027, 3026, 3026,
3024, 3023, 3023
3563, 3560, 3559,
3558, 3468, 3466
2534, 2533, 2533,
2528, 2482, 2473
4321, 1410, 1366,
1198, 1147, 1138
Table S1. The structure information, including the shortest distance between central
Fe and ligand atoms, and the vibration frequencies with most IR intensities of the
lowest-energy structures for neutral and anionic FeL4 (L = BO2, CN, NO2, NO3, OH,
CH3, NH2, BH4 and Li2H3) clusters.
1
Isomer
Fe(BO2)4
Fe(CN)4
Fe(NO2)4
Fe(NO3)4
Fe(OH)4
Fe(CH3)4
Fe(NH2)4
Fe(BH4)4
Fe(Li2H3)4
state
HOMO
(eV)
LUMO
(eV)
HL
(eV)
Isomer
B2
5
A
5
A
5
A
5
A
5
A
5
A
5
A
3
A
-9.531
-7.936
-8.211
-9.399
-8.731
-6.081
-6.404
-7.742
-4.758
-6.348
-5.185
-5.769
-7.093
-4.381
-2.877
-3.109
-3.908
-1.233
3.183
2.751
2.442
2.306
4.350
3.204
3.386
3.835
3.524
Fe(BO2)4¯
Fe(CN)4¯
Fe(NO2)4¯
Fe(NO3)4¯
Fe(OH)4¯
Fe(CH3)4¯
Fe(NH2)4¯
Fe(BH4)4¯
Fe(Li2H3)4¯
5
state
HOMO
(eV)
LUMO
(eV)
HL
(eV)
A
A
6
A
6
A
6
A
6
A
6
A
6
A
4
A
-4.884
-5.573
-4.175
-5.133
-2.008
-0.976
-0.959
-4.238
-0.697
-1.072
-1.876
-1.041
-1.430
2.391
2.424
2.486
-0.702
1.440
3.812
3.697
3.135
3.703
4.399
3.400
3.446
3.536
2.137
6
6
Table S2. Electronic state, highest occupied molecular orbital (HOMO), lowest
unoccupied molecular orbital (LUMO) and HOMO-LUMO gaps (HL) of the
lowest-energy structures for neutral and anionic FeL4 (L = BO2, CN, NO2, NO3, OH,
CH3, NH2, BH4 and Li2H3) clusters.
2
Figure S1. The low-lying isomers of neutral FeL4 (L = BO2, CN, NO2, NO3, OH, NH2,
CH3, BH4 and Li2H3) clusters along with their spin multiplicities, symmetries and
relative energies.
3
Figure S2. The low-lying isomers of anionic FeL4 (L = BO2, CN, NO2, NO3, OH,
NH2, CH3, BH4 and Li2H3) clusters along with their spin multiplicities, symmetries
and relative energies.
4
Figure S3. The ground-state structures of neutral clusters FeL4 (L = BO2, CN, NO2,
NO3, OH, CH3, NH2, BH4 and Li2H3) along with their spin multiplicities and
symmetries. The numbers in structures are the NPA charges on each atom. The red,
springgreen, royalblue, blue, olive, pink and maroon spheres represent the O, B, Fe, N,
C, H and Li atoms, respectively.
5
Figure S4. The ground-state structures of anionic clusters FeL4 (L = BO2, CN, NO2,
NO3, OH, CH3, NH2, BH4 and Li2H3) along with their spin multiplicities and
symmetries. The numbers in structures are the NPA charges on each atom. The red,
springgreen, royalblue, blue, olive, pink and maroon spheres represent the O, B, Fe, N,
C, H and Li atoms, respectively.
6
Figure S5. Calculated total spin DOS and partial spin DOS of Fe(NO3)4 [(a) and (b)],
Fe(NO2)4 [(c) and (d)], Fe(CN)4 [(e) and (f)], Fe(OH)4 [(g) and (h)], as well as
NaFe(BH4)4 [(i) and (j)]. The Fermi level is indicated by the vertical dashed line.
7
Figure S6. Calculated total spin DOS and partial spin DOS of hypersalts NaFe(NO3)4
[(a) and (b)], NaFe(NO2)4 [(c) and (d)], NaFe(CN)4 [(e) and (f)], NaFe(OH)4 [(g) and
(h)], as well as NaFe(BH4)4 [(i) and (j)]. The Fermi level is indicated by the vertical
dashed line.
8