Combining Electronic Structure Methods with the Calculation of Hydrogen Vibrational Wavefunctions: Application to Hydride Transfer in Liver Alcohol Dehydrogenase
Combining Electronic Structure Methods with the Calculation of Hydrogen Vibrational Wavefunctions: Application to Hydride Transfer in Liver Alcohol Dehydrogenase
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电子结构方法与氢振动波函数计算相结合：在肝醇脱氢酶中氢化物转移中的应用
DOI：
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发表时间：
2000
期刊：
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通讯作者：
S. Hammes‐Schiffer
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文献类型：
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作者：
S. Webb;P. Agarwal;S. Hammes‐Schiffer
本文提出了一种将电子结构方法与氢振动波函数计算相结合的计算方法的应用。本申请旨在阐明肝醇脱氢酶 (LADH) 催化的苯甲醇氧化过程中核量子力学效应的本质。氢化物从苯甲醇底物到 NAD+ 辅因子的转移由活性位点的 148 个原子模型描述。计算沿最小能量路径和直线反应路径的结构的氢化物势能曲线和相关的氢振动波函数，这些结构是通过半经验 PM3 和从头开始 RHF/3-21G 水平的电子结构计算获得的。结果表明，对于这些理论水平，氢化物转移是绝热的，并且氢隧道效应沿最小能量路径不起关键作用。相比之下，非绝热效应和氢隧道效应被证明在……
This paper presents an application of a computational approach combining electronic structure methods with the calculation of hydrogen vibrational wavefunctions. This application is directed at elucidating the nature of the nuclear quantum mechanical effects in the oxidation of benzyl alcohol catalyzed by liver alcohol dehydrogenase (LADH). The hydride transfer from the benzyl alcohol substrate to the NAD+ cofactor is described by a 148-atom model of the active site. The hydride potential energy curves and the associated hydrogen vibrational wavefunctions are calculated for structures along minimum energy paths and straight-line reaction paths obtained from electronic structure calculations at the semiempirical PM3 and ab initio RHF/3-21G levels. The results indicate that, for these levels of theory, the hydride transfer is adiabatic and hydrogen tunneling does not play a critical role along the minimum energy path. In contrast, nonadiabatic effects and hydrogen tunneling are shown to be important along t...