论文标题
使用完整的基集限制来计算高度准确的偶极矩矩
Use of the complete basis set limit for computing highly accurate ab initio dipole moments
论文作者
论文摘要
通常仅对于水（例如水）计算具有高阶基集的偶极矩。描述了一种简单而高效的策略，即用小，计算较低的基础集获得高阶偶极子。使用有限的场方法计算偶极子，可以将用较小基集计算的能量推算出来，以产生与高阶计算中获得的偶极子。该方法可将计算资源降低约50％（允许计算较大分子的可靠偶极矩计算），并同时改善了通过实验测量的红外过渡强度的一致性。对于大气上重要的分子，通常太大而无法考虑使用大型基集，则此过程将提供将计算出的光谱强度提高数％的必要手段。
Calculating dipole moments with high-order basis sets is generally only possible for the light molecules, such as water. A simple, yet highly effective strategy of obtaining high-order dipoles with small, computationally less expensive basis sets is described. Using the finite field method for computing dipoles, energies calculated with small basis sets can be extrapolated to produce dipoles that are comparable to those obtained in high order calculations. The method reduces computational resources by approximately 50% (allowing the calculation of reliable dipole moments for larger molecules) and simultaneously improves the agreement with experimentally measured infrared transition intensities. For atmospherically important molecules which are typically too large to consider the use of large basis sets, this procedure will provide the necessary means of improving calculated spectral intensities by several percent.
