Quantum Chemical Benchmark Study on 46 RNA Backbone Families Using a Dinucleotide Unit

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• 作者：Holger Kruse ; Arnost Mladek ; Konstantinos Gkionis ; Andreas Hansen ; Stefan Grimme ; Jiri Sponer
• 刊名：Journal of Chemical Theory and Computation
• 出版年：2015
• 出版时间：October 13, 2015
• 年：2015
• 卷：11
• 期：10
• 页码：4972-4991
• 全文大小：513K
• ISSN：1549-9626

文摘

We have created a benchmark set of quantum chemical structure鈥揺nergy data denoted as UpU46, which consists of 46 uracil dinucleotides (UpU), representing all known 46 RNA backbone conformational families. Penalty-function-based restrained optimizations with COSMO TPSS-D3/def2-TZVP ensure a balance between keeping the target conformation and geometry relaxation. The backbone geometries are close to the clustering-means of their respective RNA bioinformatics family classification. High-level wave function methods (DLPNO鈥揅CSD(T) as reference) and a wide-range of dispersion-corrected or inclusive DFT methods (DFT-D3, VV10, LC-BOP-LRD, M06-2X, M11, and more) are used to evaluate the conformational energies. The results are compared to the Amber RNA bsc0蠂_OL3 force field. Most dispersion-corrected DFT methods surpass the Amber force field significantly in accuracy and yield mean absolute deviations (MADs) for relative conformational energies of 鈭?.4鈥?.6 kcal/mol. Double-hybrid density functionals represent the most accurate class of density functionals. Low-cost quantum chemical methods such as PM6-D3H+, HF-3c, DFTB3-D3, as well as small basis set calculations corrected for basis set superposition errors (BSSEs) by the gCP procedure are also tested. Unfortunately, the presently available low-cost methods are struggling to describe the UpU conformational energies with satisfactory accuracy. The UpU46 benchmark is an ideal test for benchmarking and development of fast methods to describe nucleic acids, including force fields.