标题：Double proton transfer and one-electron oxidation behaviors in double H-bonded glycinamide-formamidine complex and comparison with biological base pair
作者：Li P;Bu YX;Ai HQ;Yan SH;Han KL
作者机构：[Li, P] Institute of Theoretical Chemistry, Shandong University, Jinan 250100, China, Department of Chemistry, Qufu Normal University, Qufu 273165, Ch 更多
通讯作者地址：[Bu, YX]Shandong Univ, Inst Theoret Chem, Jinan 250100, Peoples R China.
来源：The journal of physical chemistry, B. Condensed matter, materials, surfaces, interfaces & biophysical
关键词：POTENTIAL-ENERGY SURFACE;BARRIER HYDROGEN-BONDS;FORMIC-ACID DIMER;DENSITY-FUNCTIONAL THEORY;POST-HARTREE-FOCK;SEMIEMPIRICAL DYNAMICS CALCULATION;ANION MODEL SYSTEM;AB-INITIO DYNAMICS;GAS-PHASE;PEPTIDE-BOND
摘要：The behaviors of double proton transfer (DPT) occurring in a representative glycinamide-formamidine complex have been investigated employing the B3LYP/6-311++G** level of theory. Computational results suggest that the participation of a formamidine molecule favors the proceeding of the proton transfer (PT) for glycinamide compared with that without mediator-assisted case. The DPT process proceeds with a concerted mechanism rather than a stepwise one since no zwitterionic complexes have been located during the DPT process. The barrier heights are 14.4 and 3.9 kcal/mol for the forward and reverse directions, respectively. However, both of them have been reduced by 3.1 and 2.9 kcal/mol to 11.3 and 1.0 kcal/mol with further inclusion of zero-point vibrational energy (ZPVE) corrections, where the lower reverse barrier height implies that the reverse reaction should proceed easily at any temperature of biological importance. Additionally, the one-electron oxidation process for the double H-bonded glycinamide-formamidine complex has also been investigated. The oxidated product is characterized by a distonic radical cation due to the fact that one-electron oxidation takes place on glycinamide fragment and a proton has been transferred from glycinamide to formamidine fragment spontaneously. As a result, the vertical and adiabatic ionization potentials for the neutral double H-bonded complex have been determined to be about 8.46 and 7.73 eV, respectively, where both of them have been reduced by about 0.79 and 0.87 eV relative to those of isolated glycinamide due to the formation of the intermolecular H-bond with formamidine. Finally, the differences between model system and adenine-thymine base pair have been discussed briefly.