使用半随机热浴组态相互作用的激发态。
Excited states using semistochastic heat-bath configuration interaction.
机构信息
Department of Chemistry and Biochemistry, University of Colorado Boulder, Boulder, Colorado 80302, USA.
Laboratory of Atomic and Solid State Physics, Cornell University, Ithaca, New York 14853, USA.
出版信息
J Chem Phys. 2017 Oct 28;147(16):164111. doi: 10.1063/1.4998614.
We extend our recently developed heat-bath configuration interaction (HCI) algorithm, and our semistochastic algorithm for performing multireference perturbation theory, to calculate excited-state wavefunctions and energies. We employ time-reversal symmetry, which reduces the memory requirements by more than a factor of two. An extrapolation technique is introduced to reliably extrapolate HCI energies to the full CI limit. The resulting algorithm is used to compute fourteen low-lying potential energy surfaces of the carbon dimer using the cc-pV5Z basis set, with an estimated error in energy of 30-50 μHa compared to full CI. The excitation energies obtained using our algorithm have a mean absolute deviation of 0.02 eV compared to experimental values.
我们扩展了我们最近开发的热浴组态相互作用（HCI）算法，以及我们用于执行多参考微扰理论的半随机算法，以计算激发态波函数和能量。我们利用时间反演对称性，将内存需求减少了两倍以上。引入了外推技术，可可靠地将 HCI 能量外推到完全 CI 极限。所得到的算法用于计算碳二聚体的十四个低势能表面，使用 cc-pV5Z 基组，与完全 CI 相比，能量的估计误差为 30-50 μHa。与实验值相比，我们算法获得的激发能的平均绝对偏差为 0.02 eV。
Zotero 插件