Concomitant Effects of Transition Metal Chelation and Solvent Polarity on the First Molecular Hyperpolarizability of 4-Methoxyacetophenone Thiosemicarbazone: A DFT Study
Table 7
Excitation energies and wavelengths, oscillator strengths, NTO eigenvalues, and characters of the dominant electronic transitions for 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.
Medium
Molecule
Excited state
Electronic
NTO eigenvalue
E (eV)
(nm)
Gas-phase
L1
2
P H
0.8866
0.4821
4.6892
264.40
[Ni(L1)Cl2]
9
P H
0.9299
0.0342
4.1644
297.73
MLCT/LLCT
[Pd(L1)Cl2]
8
P H
0.9261
0.0557
4.1873
296.10
MLCT/LLCT
[Pt(L1)Cl2]
6
P H
0.9731
0.1224
3.8361
323.20
MLCT/LLCT
[Cu(L1)Cl2]
10
P H
1.6191
0.0330
3.4788
356.40
LMCT/LLCT
[Zn(L1)Cl2]
2
P H
0.9265
0.5390
4.7424
261.44
ILCT
DMSO
L1
2
P H
0.9190
0.7898
4.7279
262.24
/
[Ni(L1)Cl2]
8
P H
0.6493
0.3197
4.5408
273.04
LMCT/ILCT/LLCT
[Pd(L1)Cl2]
7
P H
0.8746
0.3549
4.4265
280.10
LMCT/ILCT/LLCT
[Pt(L1)Cl2]
6
P H
0.9330
0.3691
4.4592
278.04
MLCT/ILCT
[Cu(L1)Cl2]
10
P H
1.7312
0.0305
3.4829
355.98
LMCT/ILCT/LLCT
[Zn(L1)Cl2]
1
P H
0.9575
0.7015
4.5399
273.10
ILCT
stands for “particle” and H stands for “hole.” represents occupied lone pair orbitals.
