Shepard Stuart, Panadés-Barrueta Ramón L, Moroni Saverio, Scemama Anthony, Filippi Claudia
MESA+ Institute for Nanotechnology, University of Twente, 7500 AE Enschede, The Netherlands.
CNR-IOM DEMOCRITOS, Istituto Officina dei Materiali and SISSA Scuola Internazionale Superiore di Studi Avanzati, Via Bonomea 265, I-34136 Trieste, Italy.
J Chem Theory Comput. 2022 Nov 8;18(11):6722-6731. doi: 10.1021/acs.jctc.2c00769. Epub 2022 Oct 31.
We show that recently developed quantum Monte Carlo methods, which provide accurate vertical transition energies for single excitations, also successfully treat double excitations. We study the double excitations in medium-sized molecules, some of which are challenging for high-level coupled-cluster calculations to model accurately. Our fixed-node diffusion Monte Carlo excitation energies are in very good agreement with reliable benchmarks, when available, and provide accurate predictions for excitation energies of difficult systems where reference values are lacking.
我们表明，最近开发的量子蒙特卡罗方法能够为单激发提供精确的垂直跃迁能量，同时也能成功处理双激发。我们研究了中等大小分子中的双激发，其中一些分子对于高水平耦合簇计算来说，要精确建模颇具挑战性。我们的固定节点扩散蒙特卡罗激发能与现有的可靠基准非常吻合，并且能为缺乏参考值的困难系统的激发能提供准确预测。
