Analysis of Exponent Values of Gaussian-Type Functions on Quantum Protons and Deuterons in Charged or Polarized Systems
Analysis of Exponent Values of Gaussian-Type Functions on Quantum Protons and Deuterons in Charged or Polarized Systems
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DOI：
10.1002/qua.25117
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发表时间：
2016-06-15
影响因子：
2.2
通讯作者：
Udagawa, Taro
中科院分区：
文献类型：
--
作者：
Hashimoto, Marina;Ishimoto, Takayoshi;Udagawa, Taro
分析了几种带电或极化系统及其氘代物种的量子质子和氘的s型高斯型函数（GTF）中的最佳指数α值（α（opt）），该函数用于多组分分子轨道计算，包括质子和氘的核量子性质. Ishimoto及其同事（Ishimoto，Int. J. Quantum Chem.2006，106，1465）已经提出了五种中性分子的平均指数值（α（ave）），并证明了它们的α（ave）使我们能够评估H/D同位素对各种中性物质的能量和几何形状的影响。除了HeH+和HeD+分子外，几个带电或极化系统的总能量与先前的α（ave）和我们的α（opt）之间的差异仅小于总能量（0.47 kcal.mol（-1））的0.004%，而H2OH+和HeD+分子之间的相互作用能之间的差异... OH 2和H2OD+...具有先前α（ave）的OH 2系统比具有我们的α（opt）的OH 2系统小19%（0.22 kcal.mol（-1））。同时，在H2OH+中心点中心点OH 2系统中的OH键长与α（ave）和α（opt）值之间的差为0.027埃。我们还发现，在用先前的α（ave）值（α（sp））优化的几何结构处的α（opt）值的相互作用能很好地再现了用α（opt）值优化的几何结构处的相互作用能。我们已经证明，核基函数的基础上的s-型GTF与以前的α（ave）值，使我们能够评估的H/D同位素效应的能量和几何形状的充电或极化系统。(C)2016 Wiley Periodicals，Inc.
The optimal exponent alpha values (alpha(opt)) in s-type Gaussian-type functions (GTFs) for quantum protons and deuterons, which are used for multicomponent molecular orbital calculations including nuclear quantum nature of protons and deuterons, are analyzed for several charged or polarized systems and their deuterated species. Ishimoto and coworkers (Ishimoto, Int. J. Quantum Chem. 2006, 106, 1465) have already proposed the average exponent values for five neutral molecules (alpha(ave)), and demonstrated that their alpha(ave) enables us to evaluate the H/D isotope effect on energies and geometries of various neutral species. The differences between total energies of several charged or polarized systems with previous alpha(ave) and our alpha(opt) correspond to only less than 0.004% of the total energy (0.47 kcal.mol(-1)) except for HeH+ and HeD+ molecules, while the difference between interaction energies of H2OH+...OH2 and H2OD+...OH2 systems with previous alpha(ave) is 19% (0.22 kcal.mol(-1)) smaller than that with our alpha(opt). Meanwhile, the difference between OH bond lengths in H2OH+center dot center dot center dot OH2 system with alpha(ave) and alpha(opt) values is 0.027 angstrom. We also found that the interaction energies with alpha(opt) value at the geometry optimized with previous alpha(ave) value (alpha(sp)) well reproduce those at the geometry optimized with alpha(opt) value. We have demonstrated that the nuclear basis functions based on s-type GTFs with previous alpha(ave) values enable us to evaluate the H/D isotope effect on energies and geometries of charged or polarized systems. (C) 2016 Wiley Periodicals, Inc.