TY - JOUR
T1 - Determination of the oxidation potentials of organic benzene derivatives
T2 - Theory and experiment
AU - Han, Young Kyu
AU - Jung, Jaehoon
AU - Cho, Jeong Ju
AU - Kim, Hyeong Jin
PY - 2003/1/24
Y1 - 2003/1/24
N2 - We have calculated the IP, ΔG e , and E ox values for 10 mono-substituted benzene molecules and compared them with experimental values obtained by linear sweep voltammetry. The E ox values were evaluated using the density functional method and thermodynamic cycles. The relative oxidation potentials are in close agreement with experimental values, while the UB3LYP/6-31+G(d) approach shows the absolute E ox values to be lower by about 0.9 V. Consideration of bulk solvent effects is important to fully describe the experimental variation in E ox . The HOMO, NBO, and Wiberg bond index were analyzed to investigate the changes when moving from neutral to cationic molecules.
AB - We have calculated the IP, ΔG e , and E ox values for 10 mono-substituted benzene molecules and compared them with experimental values obtained by linear sweep voltammetry. The E ox values were evaluated using the density functional method and thermodynamic cycles. The relative oxidation potentials are in close agreement with experimental values, while the UB3LYP/6-31+G(d) approach shows the absolute E ox values to be lower by about 0.9 V. Consideration of bulk solvent effects is important to fully describe the experimental variation in E ox . The HOMO, NBO, and Wiberg bond index were analyzed to investigate the changes when moving from neutral to cationic molecules.
UR - http://www.scopus.com/inward/record.url?scp=0037462206&partnerID=8YFLogxK
U2 - 10.1016/S0009-2614(02)01857-2
DO - 10.1016/S0009-2614(02)01857-2
M3 - Article
AN - SCOPUS:0037462206
SN - 0009-2614
VL - 368
SP - 601
EP - 608
JO - Chemical Physics Letters
JF - Chemical Physics Letters
IS - 5-6
ER -