Structures, Electron Affinities, and Harmonic Vibrational Frequencies of C<sub>6</sub>H<sub>5</sub>X/C<sub>6</sub>H<sub>5</sub>X<sup>-</sup>
(X = N, S, NH, PH, CH<sub>2</sub>, and SiH<sub>2</sub>)
Wenguo Xu
Aifang Gao
10.1021/jp052198l.s001
https://acs.figshare.com/articles/journal_contribution/Structures_Electron_Affinities_and_Harmonic_Vibrational_Frequencies_of_C_sub_6_sub_H_sub_5_sub_X_C_sub_6_sub_H_sub_5_sub_X_sup_sup_X_N_S_NH_PH_CH_sub_2_sub_and_SiH_sub_2_sub_/3241546
The molecular structures and electron affinities of the C<sub>6</sub>H<sub>5</sub>X/C<sub>6</sub>H<sub>5</sub>X<sup>-</sup> (X = N, S, NH, PH, CH<sub>2</sub>, and SiH<sub>2</sub>)
species have been determined using seven different density functional or hybrid Hartree−Fock density functional
methods. The basis set used in this work is of double-ζ plus polarization quality with additional diffuse s-
and p-type functions, denoted DZP++. These methods have been carefully calibrated (<i>Chem. Rev.</i> <b>2002</b>,
<i>102</i>, 231). The geometries are fully optimized with each density functional theory (DFT) method, and discussed.
Harmonic vibrational frequencies were found to be within 3.2% of available experimental values for most
functionals. Three different types of the neutral−anion energy separations reported in this work are the adiabatic
electron affinity (EA<sub>ad</sub>), the vertical electron affinity (EA<sub>vert</sub>), and the vertical detachment energy (VDE). The
most reliable adiabatic electron affinities, obtained at the DZP++ BPW91 level of theory, are 1.45 (C<sub>6</sub>H<sub>5</sub>N),
2.29 (C<sub>6</sub>H<sub>5</sub>S), 1.57 (C<sub>6</sub>H<sub>5</sub>NH), 1.51 (C<sub>6</sub>H<sub>5</sub>PH), 0.91 (C<sub>6</sub>H<sub>5</sub>CH<sub>2</sub>), and 1.48 eV (C<sub>6</sub>H<sub>5</sub>SiH<sub>2</sub>), respectively.
Compared with the experimental values, the average absolute error of the BPW91 method is 0.04 eV. The
B3LYP and B3PW91 functionals also gave excellent predictions, with average absolute errors of 0.06 and
0.07 eV, respectively.
2006-01-26 00:00:00
DZP
density
Harmonic Vibrational Frequencies
VDE
PH
eV
Harmonic vibrational frequencies
EA
B 3PW functionals
CH 2
NH
3LYP
SiH 2
DFT
adiabatic electron affinity
adiabatic electron affinities
BPW 91 method