A low-cost four-component relativistic coupled cluster linear response theory based on perturbation sensitive natural spinors
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| Main Authors: | , , , |
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| Format: | Preprint |
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2025
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| _version_ | 1866908542020091904 |
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| author | Chakraborty, Sudipta Manna, Amrita Crawford, T. Daniel Dutta, Achintya Kumar |
| author_facet | Chakraborty, Sudipta Manna, Amrita Crawford, T. Daniel Dutta, Achintya Kumar |
| contents | We present an efficient implementation of four-component linear response coupled cluster singles and doubles (4c-LRCCSD) theory that enables accurate and computationally efficient calculation of polarizabilities for systems containing heavy elements. We have observed that the frozen natural spinor (FNS)-based truncation scheme is not suitable for linear response properties, as it leads to larger errors in static and dynamic polarizability values. In this work, we have introduced a "perturbation-sensitive" density to construct the natural spinor basis, termed FNS++. Using FNS++, we achieve excellent accuracy when compared to experimental data and other theoretical results, even after truncating nearly 70% of the total virtual spinors. We also present pilot applications of 4c-LRCCSD with a canonical basis to calculate the polarizability spectra of 3d transition metals. By employing the FNS++-based 4c-LRCCSD, we have been able to compute polarizabilities for systems with over 1200 virtual spinors, maintaining low computational cost and excellent accuracy. |
| format | Preprint |
| id |
arxiv_https___arxiv_org_abs_2503_23144 |
| institution | arXiv |
| publishDate | 2025 |
| record_format | arxiv |
| spellingShingle | A low-cost four-component relativistic coupled cluster linear response theory based on perturbation sensitive natural spinors Chakraborty, Sudipta Manna, Amrita Crawford, T. Daniel Dutta, Achintya Kumar Chemical Physics We present an efficient implementation of four-component linear response coupled cluster singles and doubles (4c-LRCCSD) theory that enables accurate and computationally efficient calculation of polarizabilities for systems containing heavy elements. We have observed that the frozen natural spinor (FNS)-based truncation scheme is not suitable for linear response properties, as it leads to larger errors in static and dynamic polarizability values. In this work, we have introduced a "perturbation-sensitive" density to construct the natural spinor basis, termed FNS++. Using FNS++, we achieve excellent accuracy when compared to experimental data and other theoretical results, even after truncating nearly 70% of the total virtual spinors. We also present pilot applications of 4c-LRCCSD with a canonical basis to calculate the polarizability spectra of 3d transition metals. By employing the FNS++-based 4c-LRCCSD, we have been able to compute polarizabilities for systems with over 1200 virtual spinors, maintaining low computational cost and excellent accuracy. |
| title | A low-cost four-component relativistic coupled cluster linear response theory based on perturbation sensitive natural spinors |
| topic | Chemical Physics |
| url | https://arxiv.org/abs/2503.23144 |