Efficient correlation-corrected vibrational self-consistent field computation of OH-stretch frequencies using a low-scaling algorithm

摘要

The authors present a new computational scheme to perform accurate and fast direct correlation-corrected vibrational self-consistent field (CC-VSGF) computations for a selected number of vibrational modes,which is aimed at predicting a few vibrations in large molecular systems.The method is based on a systematic selection of vibrational mode-mode coupling terms,leading to the direct ab initio construction of a sparse potential energy surface.The computational scaling of the CC-VSCF computation on the generated surface is then further reduced by using a screening procedure for the correlation-correction contributions.The proposed method is applied to the computation of the OH-stretch frequency of five aliphatic alcohols.The authors investigate the influence of different pseudopotential and all-electron basis sets on the quality of the correlated potential energy surfaces computed and on the OH-stretch frequencies calculated for each surface.With the help of these test systems,the authors show that their method offers a computational scaling that is two orders of magnitude lower than a standard CC-VSCF method and that it is of equal accuracy.