Anoop Ajaya Kumar Nair, Julian Bessner, Timo Jacob, Elvar Örn Jónsson
{"title":"Advanced perturbation scheme for efficient polarizability computations","authors":"Anoop Ajaya Kumar Nair, Julian Bessner, Timo Jacob, Elvar Örn Jónsson","doi":"arxiv-2409.10184","DOIUrl":null,"url":null,"abstract":"We present an efficient momentum based perturbation scheme to evaluate\npolarizability tensors of small molecules and at the fraction of the\ncomputational cost compared to conventional energy based perturbation schemes.\nFurthermore, the simplicity of the scheme allows for the seamless integration\ninto modern quantum chemistry codes. We apply the method to systems where the\nwavefunctions are described on a real-space grid and are therefore not subject\nto finite size basis set errors. In the grid-based scheme errors can be\nattributed to the resolution and the size of the grid-space. The applicability\nand generality of the method is exhibited by calculating polarizability tensors\nincluding the dipole-dipole and up to the quadrupole-quadrupole for a series of\nsmall molecules, representing the most common symmetry groups. By a direct\ncomparison with standard techniques based on energy perturbation we show that\nthe method reduces the number of explicit computations by a factor of 30.\nNumerical errors introduced due to the arrangement of the explicit point\ncharges are eliminated with an extrapolation scheme to the effective\nzero-perturbation limit.","PeriodicalId":501304,"journal":{"name":"arXiv - PHYS - Chemical Physics","volume":null,"pages":null},"PeriodicalIF":0.0000,"publicationDate":"2024-09-16","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"","citationCount":"0","resultStr":null,"platform":"Semanticscholar","paperid":null,"PeriodicalName":"arXiv - PHYS - Chemical Physics","FirstCategoryId":"1085","ListUrlMain":"https://doi.org/arxiv-2409.10184","RegionNum":0,"RegionCategory":null,"ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"","JCRName":"","Score":null,"Total":0}
引用次数: 0
Abstract
We present an efficient momentum based perturbation scheme to evaluate
polarizability tensors of small molecules and at the fraction of the
computational cost compared to conventional energy based perturbation schemes.
Furthermore, the simplicity of the scheme allows for the seamless integration
into modern quantum chemistry codes. We apply the method to systems where the
wavefunctions are described on a real-space grid and are therefore not subject
to finite size basis set errors. In the grid-based scheme errors can be
attributed to the resolution and the size of the grid-space. The applicability
and generality of the method is exhibited by calculating polarizability tensors
including the dipole-dipole and up to the quadrupole-quadrupole for a series of
small molecules, representing the most common symmetry groups. By a direct
comparison with standard techniques based on energy perturbation we show that
the method reduces the number of explicit computations by a factor of 30.
Numerical errors introduced due to the arrangement of the explicit point
charges are eliminated with an extrapolation scheme to the effective
zero-perturbation limit.