Gómez-Sandoval Z, Calaminici P, Köster A M, Lotina-Hennsen B, King-Díaz B, Macías-Ruvalcaba N, Aguilar-Martínez M, Jiménez-Estrada M
Departamento de Química, CINVESTAV, Avenida Instituto Politécnico Nacional 2508, A.P. 14-740 México D.F. 07000, México, Facultad de Química, Departamentos de Bioquímica y Fisicoquímica, Universidad Nacional Autónoma de México, Ciudad Universitaria, México D.F. 04510, México, and Instituto de Química, Universidad Nacional Autónoma de México, Ciudad Universitaria, México D.F. 04510, México.
J Chem Theory Comput. 2007 May;3(3):894-904. doi: 10.1021/ct6003356.
The molecular and electronic structures of a series of 2-[(R-phenyl)amine]-1,4-naphthalenediones (R = m-Me, p-Me, m-Et, p-CF3, p-Hex, p-Et, m-F, m-Cl, p-OMe, p-COMe, p-Bu, m-COOH, p-Cl, p-COOH, p-Br, m-NO2, m-CN, and p-NO2) and their anions are investigated in the framework of density functional theory. The calculations are of all-electron type using a double zeta valence polarization basis set optimized for density functional theory methods. The theoretical study shows that all compounds are nonplanar. The nonplanarity can be rationalized in terms of occupied π orbitals. A linear correlation between the measured half-wave potentials and the calculated gas-phase electron affinities is found. It holds for local as well as generalized gradient corrected functionals. Structural parameters, harmonic vibrational frequencies, and adiabatic and vertical electron affinities as well as orbital and spin density plots of the studied compounds are presented.
在密度泛函理论框架下，研究了一系列2-[(R-苯基)胺]-1,4-萘二酮（R = 间甲基、对甲基、间乙基、对三氟甲基、对己基、对乙基、间氟、间氯、对甲氧基、对乙酰基、对丁基、间羧基、对氯、对羧基、对溴、间硝基、间氰基和对硝基）及其阴离子的分子和电子结构。计算采用全电子类型，使用针对密度泛函理论方法优化的双ζ价极化基组。理论研究表明，所有化合物均为非平面结构。非平面性可以根据占据的π轨道进行合理解释。发现测量的半波电位与计算的气相电子亲和能之间存在线性相关性。这适用于局部以及广义梯度校正泛函。给出了所研究化合物的结构参数、简谐振动频率、绝热和垂直电子亲和能以及轨道和自旋密度图。
