Supporting Information

Interactions of hydrogen molecules with complexes of lithium cation and aromatic nitrogen-containing heterocyclic anions

Yingxin Sun,*† and Huai Sun*††

†School of Chemical and Environmental Engineering, Shanghai Institute of Technology,

†† School of Chemistry and Chemical Engineering and Key Laboratory for Thin Film and Microfabrication of Ministry of Education,

Shanghai Jiao Tong University, Shanghai 200240, China

E-mail: , and


Table S1 The total, average and increment hydrogen binding energies (in kJ/mol) of H2 molecules with cyclopentadienide C5H5- and C5H5-Li at RI-MP2/cc-pVQZ methods, respectively

n (H2) / cyclopentadienide C5H5- / C5H5-Li
Total / Ave / Incr. / Total / Ave / Incr.
1 / 14.34 / 14.34 / - / 12.23 / 12.23 / -
2 / 28.10 / 14.05 / 13.76 / 17.62 / 8.81 / 5.38
3 / 21.26 / 7.09 / 3.64
4 / 27.41 / 6.85 / 6.16


Table S2 The total, average and increment hydrogen binding energies (in kJ/mol) of H2 molecules with pyrrolide C4H4N- and C4H4N-Li at RI-MP2/cc-pVQZ methods, respectively

n (H2) / pyrrolide C4H4N- / in-plane C4H4N-Li / out-of-plane C4H4N-Li
Total / Ave / Incr. / Total / Ave / Incr. / Total / Ave / Incr.
1 / 10.71 / 10.71 / - / 11.86 / 11.86 / - / 12.04 / 12.04 / -
2 / 19.89 / 9.95 / 9.18 / 27.35 / 13.67 / 15.49 / 21.66 / 10.83 / 9.62
3 / 32.02 / 10.67 / 12.13 / 39.29 / 13.10 / 11.94 / 25.63 / 8.54 / 3.97
4 / 43.80 / 10.95 / 11.78 / 50.82 / 12.71 / 11.53 / 29.97 / 7.49 / 4.34
5 / 56.52 / 11.30 / 5.69 / 35.22 / 7.04 / 5.26
6 / 65.92 / 10.99 / 9.40 / 39.90 / 6.65 / 4.68
7 / 73.85 / 10.55 / 7.92


Table S3 The total, average and increment hydrogen binding energies (in kJ/mol) of H2 molecules with pyrazolide C3H3N2- and the corresponding C3H3N2-Li at RI-MP2/cc-pVQZ methods, respectively

n (H2) / pyrazolide C3H3N2- / in-plane C3H3N2-Li / out-of-plane C3H3N2-Li
Total / Ave / Incr. / Total / Ave / Incr. / Total / Ave / Incr.
1 / 10.44 / 10.44 / - / 10.55 / 10.55 / - / 13.27 / 13.27 / -
2 / 20.17 / 10.08 / 9.73 / 19.30 / 9.65 / 8.75 / 22.53 / 11.27 / 9.26
3 / 29.05 / 9.68 / 8.88 / 28.80 / 9.60 / 9.50 / 29.86 / 9.95 / 7.32
4 / 37.50 / 9.38 / 8.45 / 35.19 / 8.80 / 6.39 / 33.96 / 8.49 / 4.10
5 / 47.55 / 9.51 / 10.05 / 38.77 / 7.75 / 3.58 / 38.09 / 7.62 / 4.13
6 / 58.01 / 9.67 / 10.46 / 42.52 / 7.09 / 3.75 / 43.88 / 7.31 / 5.79
7 / 47.29 / 6.76 / 4.77 / 46.19 / 6.60 / 2.31
8 / 56.01 / 7.00 / 8.71 / 51.56 / 6.44 / 5.37
9 / 59.80 / 6.64 / 3.80
10 / 63.64 / 6.36 / 3.84


Table S4 The total, average and increment hydrogen binding energies (in kJ/mol) of H2 molecules with imidazolide C3H3N2- and the corresponding C3H3N2-Li at RI-MP2/cc-pVQZ methods, respectively

n (H2) / imidazolide C3H3N2- / in-plane C3H3N2-Li / out-of-plane C3H3N2-Li
Total / Ave / Incr. / Total / Ave / Incr. / Total / Ave / Incr.
1 / 9.62 / 9.62 / - / 12.30 / 12.30 / - / 13.09 / 13.09 / -
2 / 18.96 / 9.48 / 9.34 / 27.05 / 13.52 / 14.75 / 24.94 / 12.47 / 11.85
3 / 27.25 / 9.08 / 8.29 / 39.44 / 13.15 / 12.39 / 30.11 / 10.04 / 5.17
4 / 35.23 / 8.81 / 7.98 / 50.37 / 12.59 / 10.93 / 34.23 / 8.56 / 4.12
5 / 45.14 / 9.03 / 9.91 / 56.04 / 11.21 / 5.67 / 38.29 / 7.66 / 4.06
6 / 54.86 / 9.14 / 9.72 / 61.11 / 10.19 / 5.07 / 41.92 / 6.99 / 3.63
7 / 65.71 / 9.39 / 4.60 / 45.75 / 6.54 / 3.83
8 / 73.52 / 9.19 / 7.80 / 50.58 / 6.32 / 4.83
9 / 80.16 / 8.91 / 6.64


Table S5 The total, average and increment hydrogen binding energies (in kJ/mol) of H2 molecules with 1, 2, 3-triazolide C2H2N3- and the corresponding 1, 2, 3-C3H3N2-Li at RI-MP2/cc-pVQZ methods, respectively

n (H2) / 1, 2, 3-triazolide C2H2N3- / in-plane 1, 2, 3-C2H2N3-Li / out-of-plane 1, 2, 3-C2H2N3-Li
Total / Ave / Incr. / Total / Ave / Incr. / Total / Ave / Incr.
1 / 9.18 / 9.18 / - / 11.28 / 11.28 / - / 13.20 / 13.20 / -
2 / 18.42 / 9.21 / 9.24 / 21.09 / 10.54 / 9.81 / 25.75 / 12.87 / 12.55
3 / 26.89 / 8.96 / 8.47 / 31.18 / -0.39 / 10.09 / 33.29 / 11.10 / 7.54
4 / 34.37 / 8.59 / 7.48 / 37.54 / 9.38 / 6.36 / 36.89 / 9.22 / 3.60
5 / 42.11 / 8.42 / 7.74 / 42.87 / 8.57 / 5.33 / 40.57 / 8.11 / 3.68
6 / 49.14 / 8.19 / 7.03 / 47.31 / 7.89 / 4.44 / 44.21 / 7.37 / 3.64
7 / 57.66 / 8.24 / 8.51 / 50.52 / 7.22 / 3.20 / 47.55 / 6.79 / 3.35
8 / 66.21 / 8.28 / 8.55 / 53.88 / 6.74 / 3.37 / 51.18 / 6.40 / 3.63
9 / 60.00 / 6.67 / 6.12 / 55.54 / 6.17 / 4.36
10 / 65.21 / 6.52 / 5.20 / 60.28 / 6.03 / 4.74
11 / 69.75 / 6.34 / 4.54


Table S6 The total, average and increment hydrogen binding energies (in kJ/mol) of H2 molecules with 1, 2, 4-triazolide C2H2N3- and the corresponding 1, 2, 4-C3H3N2-Li at RI-MP2/cc-pVQZ methods, respectively

n (H2) / 1, 2, 4-triazolide C2H2N3- / in-plane (I)
1, 2, 4-C2H2N3-Li / in-plane (II)
1, 2, 4-C2H2N3-Li / out-of-plane
1, 2, 4-C2H2N3-Li
Total / Ave / Incr. / Total / Ave / Incr. / Total / Ave / Incr. / Total / Ave / Incr.
1 / 9.15 / 9.15 / - / 12.85 / 12.85 / - / 11.12 / 11.12 / - / 13.70 / 13.70 / -
2 / 18.04 / 9.02 / 8.89 / 26.80 / 13.40 / 13.95 / 20.46 / 10.23 / 9.34 / 24.15 / 12.08 / 10.45
3 / 26.13 / 8.71 / 8.10 / 39.86 / 13.29 / 13.06 / 30.46 / 10.15 / 10.00 / 34.45 / 11.48 / 10.30
4 / 33.17 / 8.29 / 7.04 / 50.29 / 12.57 / 10.43 / 37.03 / 9.26 / 6.57 / 37.64 / 9.41 / 3.19
5 / 40.71 / 8.14 / 7.54 / 55.91 / 11.18 / 5.63 / 41.01 / 8.20 / 3.98 / 40.70 / 8.14 / 3.06
6 / 47.84 / 7.97 / 7.13 / 60.80 / 10.13 / 4.89 / 44.62 / 7.44 / 3.61 / 43.85 / 7.31 / 3.15
7 / 56.16 / 8.02 / 8.32 / 65.57 / 9.37 / 4.77 / 50.23 / 7.18 / 5.61 / 48.07 / 6.87 / 4.22
8 / 64.46 / 8.06 / 8.30 / 69.84 / 8.73 / 4.28 / 55.69 / 6.96 / 5.46 / 51.49 / 6.44 / 3.42
9 / 74.00 / 9.25 / 4.16 / 58.70 / 6.52 / 3.01 / 55.24 / 6.14 / 3.75
10 / 83.22 / 8.32 / 9.22 / 61.89 / 6.19 / 3.18 / 60.72 / 6.07 / 5.48
11 / 86.75 / 7.89 / 3.53 / 65.26 / 5.93 / 3.37
12 / 68.73 / 5.73 / 3.47


Table S7 The total, average and increment hydrogen binding energies (in kJ/mol) of H2 molecules with tetrazolide CHN4- and the corresponding CHN4-Li at RI-MP2/cc-pVQZ methods, respectively

n (H2) / tetrazolide CHN4- / in-plane (I) CHN4-Li / in-plane (II) CHN4-Li / out-of-plane CHN4-Li
Total / Ave / Incr. / Total / Ave / Incr. / Total / Ave / Incr. / Total / Ave / Incr.
1 / 8.36 / 8.36 / - / 11.90 / 11.90 / - / 12.16 / 12.16 / - / 13.81 / 13.81 / -
2 / 16.33 / 8.17 / 7.98 / 22.95 / 11.47 / 11.05 / 22.64 / 11.32 / 10.47 / 27.55 / 13.78 / 13.74
3 / 23.90 / 7.97 / 7.56 / 33.49 / 11.16 / 10.54 / 33.17 / 11.06 / 10.54 / 37.85 / 12.62 / 10.30
4 / 31.21 / 7.80 / 7.32 / 40.17 / 10.04 / 6.68 / 40.01 / 10.00 / 6.84 / 41.02 / 10.25 / 3.17
5 / 37.50 / 7.50 / 6.29 / 44.96 / 8.99 / 4.79 / 44.96 / 8.99 / 4.95 / 44.36 / 8.87 / 3.34
6 / 43.72 / 7.29 / 6.22 / 49.56 / 8.26 / 4.60 / 47.80 / 7.97 / 2.84 / 47.46 / 7.91 / 3.10
7 / 50.48 / 7.21 / 6.76 / 53.33 / 7.62 / 3.76 / 51.27 / 7.32 / 3.47 / 51.27 / 7.32 / 3.82
8 / 56.38 / 7.05 / 5.90 / 57.23 / 7.15 / 3.91 / 57.48 / 7.18 / 6.21 / 54.35 / 6.79 / 3.07
9 / 63.32 / 7.04 / 6.93 / 62.09 / 6.90 / 4.86 / 60.38 / 6.71 / 2.90 / 60.40 / 6.71 / 6.05
10 / 70.08 / 7.01 / 6.76 / 66.99 / 6.70 / 4.90 / 64.03 / 6.40 / 3.65 / 62.07 / 6.21 / 1.67
11 / 70.06 / 6.37 / 3.07 / 69.57 / 6.32 / 5.54 / 64.85 / 5.90 / 2.78
12 / 73.35 / 6.11 / 3.30 / 72.39 / 6.03 / 2.82 / 68.59 / 5.72 / 3.74
13 / 76.46 / 5.88 / 3.11 / 75.80 / 5.83 / 3.41
14 / 79.66 / 5.69 / 3.20 / 79.33 / 5.67 / 3.53


Table S8 Binding energies of one hydrogen molecule with tetrazolide (CHN4-) anion, calculated at different levels of theory by introducing diffusion function (aug-)

Methods / CHN4-(1H2)
B3LYP/6-31+G(d,p) / 6.1
MP2/6-311++G(2d,2p) / 6.8
RI-MP2/TZVPP / 8.0
RI-MP2/QZVPP / 8.2
RI-MP2/cc-pVTZ / 8.2
RI-MP2/aug-cc-pVTZ / 7.9
RI-MP2/cc-pVQZ / 8.4
RI-MP2/aug-cc-pVQZ / 8.1
RI-MP2/CBS / 8.5
RI-MP2/CBS(aug-) / 8.2
CCSD(T)/TZVPP / 7.7
CCSD(T)/cc-pVQZ / 8.2
CCSD(T)/CBS / 8.3
CCSD(T)/CBS(aug-) / 8.3


Table S9 The initial force field in previous work and the modified force field in this work obtained by fitting higher level ab initio data

Li parameters / Initial FF / Modified FF
r0 (Å) / 2.0 / 2.3
ε (kcal/mol) / 0.005 / 0.0004

Fig. S1 RI-MP2/TZVPP optimized structures of clusters of H2 molecules and CnHnN5-n- [n = 1-5] anions


C5H5-Li in-plane C4H4N-Li out-of-plane C4H4N-Li

in-plane pyrazolide C3H3N2-Li out-of-plane pyrazolide C3H3N2-Li

in-plane imidazolide C3H3N2-Li out-of-plane imidazolide C3H3N2-Li

in-plane 1, 2, 3-C2H2N3-Li out-of-plane 1, 2, 3-C2H2N3-Li

in-plane (I) 1, 2, 4-C2H2N3-Li in-plane (II) 1, 2, 4-C2H2N3-Li

out-of-plane 1, 2, 4-C2H2N3-Li in-plane (I) CHN4-Li

in-plane (II) CHN4-Li out-of-plane CHN4-Li

Fig. S2 RI-MP2/TZVPP optimized structures of adsorption complexes with the maximum number of adsorbed H2 over different lithium salts. The yellow balls indicate adsorbed H2 molecules interacting with the Li+ cation



Fig. S3 RI-MP2/TZVPP optimized structures of adsorption complexes in-plane (I) CHN4-Li-nH2 with the number of adsorbed H2 increasing from one to fourteen. The yellow balls indicate adsorbed H2 molecules interacting with the Li+ cation

Fig. S4 The interaction energy curves between hydrogen molecule and Li cation in in-plane Li-CHN4, the X atom is a ghost atom placed at the center of mass of H2

S1