Geometries and chemical structures of TC1 [(a) and (b)] and TPAR1 [(c) and (d)] in both free and bound states. Geometries were optimized under the level of B3LYP/6-311G(d,p). The free dyes possess typical donor--anchor structures and the bound dyes possess donor--anchor-Ti complex structures.
(a) IR spectra of neat TC1 and anchored TC1 on film. (b) IR spectra of neat TPAR1 and anchored TPAR1 on film. (c) Calculated IR spectra of free TC1 and under the level of B3LYP/6-311G(d,p). (d) Calculated IR spectra of free TPAR1 and under the level of B3LYP/6-311G(d,p). The blue block indicates the change of the vibration of carboxyl group before and after bound to . The insets in [(a) and (b)] are the photographs of the neat dyes and the dyes anchored films.
Effects of (a) basis sets and(b) functionals on the energy evaluation of frontier orbitals of TC1 (blue) and TPAR1 (red). (a) has been given with the functional of B3LYP while (b) has been given with the basis set of 6-31G(d,p).
Optimized geometries and dipole moments of TC1/TPAR1 in the free and bound states. (a) TC1; (b) bound TC1; (c) TPAR1; (d) bound TPAR1; and (e) schematic difference of vertical dipole moments of TC1 and TPAR1 when anchored to a surface. The lengths of the arrows denoted the relative values of dipole moments. The angle between surface and a dye dipole were measured roughly from the schematics.
Experimental (red line) and theoretical (black line) spectra of TC1 and TPAR1 in free form and bound to . (a) TC1; (b) bound TC1; (c) TPAR1; and (d) bound TPAR1.
Frontier molecular orbitals of (a) free TC1, (b) bound TC1, (c) free TPAR1, and (d) bound TPAR1.
TDOSs and PDOSs for (a) free TC1, (b) bound TC1, (c) free TPAR1, and (d) bound TPAR1. The insets show the amplification of the LUMO of bound dyes.
TDOSs of TC1/TPAR1, and their corresponding TDOS deviation after bound to Ti complex. (a) TDOS of TC1 before and after bound to Ti complex; (b) TDOS of TPAR1 before and after bound to Ti complex; (c) TDOS deviation of TC1 after bound to Ti complex; and (d) TDOS deviation of TPAR1 after bound to Ti complex. The PDOSs of Ti complex in the bound TC1/TPAR1 have also been included to investigate the effects of the Ti complex on the electronic states of the dyes.
Functional and basis set effects on the geometry parameters of TC1 and TPAR1. L: bond lengths (Å); A: bond angles (°); and D: dihedral angles (°). The bond lengths in parenthesis are MP2/6-31G(d,p) values of triarylamine-base dyes published in Ref. 15.
Basis set effects on of TC1 (in nanometers). The same basis set is used for geometry optimization and UV spectra determination. All calculations have been performed in gas phase with the B3LYP functional.
Functionals effect on excitations of TC1 and TPAR1. maximum absorption wavelength. E excitation energy. transition dipole moment. The main configuration of maximum absorption wavelengths of TC1 and TPAR1 within all the as-investigated methods is the transition from HOMO to LUMO. The experimental values of maximum absorption wavelengths of TC1 and TPAR1 are 400 and 458 nm in methanol, respectively (Refs. 9 and 10).
Geometry parameters of TC1, Bound TC1, TPAR1, and Bound TPAR1. L: bond lengths (Å); A: bond angles (°); and D: dihedral angles (°).
Excitations of TC1 and TPAR1 in both free and bound states. excitation wavelength; E: excitation energy; and : oscillator strengths.
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