Excitation and ionization energies of substituted anilines calculated with density functional theory
Orbital: The Electronic Journal of Chemistry
Excitation and ionization energies of substituted anilines calculated with density functional theory
Autor Correspondente: Yuji Takahata | [email protected]
Palavras-chave: singlet excitation energy, ionization energy, cebe, density functional theory, substituted anilines
Resumos Cadastrados
Resumo Inglês:
Valence electron singlet excitation energies (VEExE), valence electron
ionization energies (VEIE), core electron binding energies (CEBE), and non-resonant Xray emission energies of substituted anilines and related molecules were calculated using
density functional theory (DFT). The energy calculations were done with TZP basis set of
Slater Type Orbitals. PW86x-PW91c, turned out to be the best XC functional among eight
functionals tested for time dependent DFT (TDDFT) calculation of the singlet excitation
energies of the substituted anilines. Using the XC functional, average absolute deviation
(AAD) from experiment was 0.223 eV for eighteen cases with maximum absolute
deviation of 0.932 eV. The valence electron ionization energies of the substituted
benzenes were calculated by ΔSCF method with PW86x-PW91c. AAD from experiment
was 0.21 eV. The CEBEs were calculated with the previously established method, named
as scheme 2003. ΔCEBE(SMS),, sum of mono substituted (SMS) CEBE shift, and mutual
interference effect (MIE) were defined and their values were calculated. Magnitude of MIE
provides the degree of mutual interference between two substituents in a phenyl ring.
Average absolute value of MIE was ca. 0.1 eV for the three isomers of phenetidine. Using
the calculated valence electron ionization energies and the core electron binding energies
of one of the phenetidines, some X-ray emission energies were calculated.
