短程和长程交换对DNA单体，堆积复合物和Watson-Crick对的各种激发态特性的重要性,Journal of Chemical Theory and Computation

当前位置： X-MOL 学术 › J. Chem. Theory Comput. › 论文详情

Our official English website, www.x-mol.net, welcomes your feedback! (Note: you will need to create a separate account there.)

短程和长程交换对DNA单体，堆积复合物和Watson-Crick对的各种激发态特性的重要性
Journal of Chemical Theory and Computation ( IF 5.7 ) Pub Date : 2015-04-06 00:00:00 , DOI: 10.1021/acs.jctc.5b00105
Alexandra E. Raeber ₁ , Bryan M. Wong ₁

Affiliation

我们提出了几种时间相关的DFT（TD-DFT）方法的详细分析，包括常规的杂合功能和两种非经验性调节范围分隔的功能，用于预测DNA核碱基单体和二聚体中的各种电子激发。这套庞大而广泛的激发包括总共50个不同的跃迁（每个跃迁经过测试的DFT功能），包括几个n→π和π→π*价激发，远距离电荷转移激发和扩展的Rydberg跃迁（完成自高级EOM-CCSD（T）方法的基准计算）。这些系统中存在局部化合价激发以及极端的远距离电荷转移激发，对TD-DFT方法提出了严峻的挑战，该方法使我们能够评估短时和长时交换贡献对于同时预测所有物质的重要性。这些不同的过渡。特别是，我们发现不具备这两种功能的功能短程和全程远程交换组件无法以相同的精度预测不同类型的核碱基激发。最重要的是，当前的研究强调了短距离交换和长距离交换的非经验调整贡献对于准确预测这些具有挑战性的核碱基系统中各种激发的重要性。

"点击查看英文标题和摘要"

The Importance of Short- and Long-Range Exchange on Various Excited State Properties of DNA Monomers, Stacked Complexes, and Watson–Crick Pairs

We present a detailed analysis of several time-dependent DFT (TD-DFT) methods, including conventional hybrid functionals and two types of nonempirically tuned range-separated functionals, for predicting a diverse set of electronic excitations in DNA nucleobase monomers and dimers. This large and extensive set of excitations comprises a total of 50 different transitions (for each tested DFT functional) that includes several n → π and π → π* valence excitations, long-range charge-transfer excitations, and extended Rydberg transitions (complete with benchmark calculations from high-level EOM-CCSD(T) methods). The presence of localized valence excitations as well as extreme long-range charge-transfer excitations in these systems poses a serious challenge for TD-DFT methods that allows us to assess the importance of both short- and long-range exchange contributions for simultaneously predicting all of these various transitions. In particular, we find that functionals that do not have both short- and full long-range exchange components are unable to predict the different types of nucleobase excitations with the same accuracy. Most importantly, the current study highlights the importance of both short-range exchange and a nonempirically tuned contribution of long-range exchange for accurately predicting the diverse excitations in these challenging nucleobase systems.

更新日期：2015-04-06

点击分享查看原文

点击收藏

公开下载

阅读更多本刊新发论文本刊介绍/投稿指南