Theoretical Study of the Ionization of Phenol−Water and Phenol−Ammonia Hydrogen-Bonded Complexes
Theoretical Study of the Ionization of Phenol−Water and Phenol−Ammonia Hydrogen-Bonded Complexes
复制标题
苯酚-水和苯酚-氨氢键配合物电离的理论研究
DOI：
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发表时间：
1997
期刊：
影响因子：
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通讯作者：
J. Bertrán
中科院分区：
文献类型：
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作者：
M. Sodupe;A. Oliva;J. Bertrán
苯酚-水和苯酚-氨络合物的电离已使用从头计算方法（包括电子相关法和混合三参数 B3LYP 密度泛函方法）测定。苯酚-水阳离子最稳定的结构对应于C6H5OH+-H2O非质子转移络合物。然而，对于苯酚-氨阳离子，计算表明势能表面上唯一的最小值对应于 C6H5O-NH4+ 质子转移形式。计算出的 C6H5OH−H2O 和 C6H5OH−NH3 的 B3LYP 绝热电离势分别为 7.65 和 7.33 eV。获得的结果表明，对于中性氢键体系，B3LYP 密度泛函方法产生的结果与从头算 MP2 或 MCPF 方法获得的结果非常相似。然而，对于电离自由基阳离子，B3LYP 结果与实验和 MCPF 方法相比，比 UMP2 好得多。未标度的 B3LYP 振动频率非常一致...
The ionization of phenol−water and phenol−ammonia complexes have been determined both using ab initio methods that include electron correlation and the hybrid three-parameter B3LYP density functional method. The most stable structure of phenol−water cation corresponds to the C6H5OH+−H2O non-proton-transferred complex. However, for the phenol−ammonia cation the calculations indicate that the only minimum on the potential energy surface corresponds to the C6H5O−NH4+ proton transferred form. The computed B3LYP adiabatic ionization potentials for C6H5OH−H2O and C6H5OH−NH3 have been determined to be 7.65 and 7.33 eV, respectively. The results obtained indicate that, for the neutral H-bonded systems, the B3LYP density functional method yields very similar results to those obtained with the ab initio MP2 or MCPF methods. However, for the ionized radical cations, B3LYP results compare much better with experiment and to the MCPF method than UMP2. The unscaled B3LYP vibrational frequencies are in very good agreemen...