Concomitant Effects of Transition Metal Chelation and Solvent Polarity on the First Molecular Hyperpolarizability of 4-Methoxyacetophenone Thiosemicarbazone: A DFT Study
Table 6
Natural transition orbitals (NTOs) compositions for the thione tautomer of MAPTSC and its complexesin gas-phase and DMSO, calculated at the TD-DFT/CAM-B3LYP/6-31++G(d,p)/(SDD for metal ions) level of theory.
Molecule
NTOs
Orbital compositions of fragments (%)
Main distribution of NTOs on molecular systems
2
Gas-phase
L1
Hole
—
36.496
63.504
—
MAP + TSC
Particle
—
13.856
86.144
—
TSC
Ni(L1)Cl2
Hole
4.537
50.724
43.388
1.351
MAP + TSC
Particle
46.092
2.627
9.700
41.581
Ni(II) ion + 2
Pd(L1)Cl2
Hole
3.958
49.695
45.108
1.239
MAP + TSC
Particle
32.732
4.901
6.195
56.172
Pd(II) ion + 2
Pt(L1)Cl2
Hole
5.517
43.596
49.385
1.501
MAP + TSC
Particle
56.516
5.890
7.933
29.661
Pt(II) ion + 2
Cu(L1)Cl2
Hole
59.034
3.915
11.890
25.160
Cu(II) ion + 2
Particle
8.056
3.214
66.050
22.679
TSC + 2
Zn(L1)Cl2
Hole
1.873
45.358
51.649
1.119
MAP + TSC
Particle
1.731
34.905
57.951
5.413
MAP + TSC
DMSO
L1
Hole
—
41.677
58.323
—
MAP + TSC
Particle
—
29.818
70.182
—
MAP + TSC
Ni(L1)Cl2
Hole
19.896
37.686
36.486
5.932
Ni(II) ion + MAP + TSC
Particle
6.189
40.681
35.610
17.520
MAP + TSC + 2
Pd(L1)Cl2
Hole
34.365
25.958
24.693
14.984
Pd(II) ion + MAP + TSC + 2
Particle
1.806
61.076
23.100
14.018
MAP + TSC + 2
Pt(L1)Cl2
Hole
5.065
60.271
33.556
1.108
MAP + TSC
Particle
30.291
52.437
12.099
5.173
Pt(II) ion + MAP
Cu(L1)Cl2
Hole
61.952
2.016
17.871
18.162
Cu(II) ion + TSC + 2
Particle
9.275
22.645
20.973
47.107
MAP + TSC + 2
Zn(L1)Cl2
Hole
1.932
61.449
35.673
0.945
MAP + TSC
Particle
0.714
70.615
27.791
0.880
MAP + TSC
(II) represents the transition metal ions. is the 4-methoxyacetophenone moiety. is the thiosemicarbazones moiety.
