Tiago Leyser da Costa Gouveia, , , Lucas Lang, , , Dimitrios Maganas, , and , Frank Neese*,
{"title":"一般自旋受限开壳组态相互作用单峰(GS-ROCIS):用于计算磁耦合过渡金属系统的光和x射线吸收和磁圆二色谱的自旋轨道耦合和塞曼算符的实现。","authors":"Tiago Leyser da Costa Gouveia, , , Lucas Lang, , , Dimitrios Maganas, , and , Frank Neese*, ","doi":"10.1021/acs.jpca.5c05086","DOIUrl":null,"url":null,"abstract":"<p >In this paper we present the theory and implementation of the spin–orbit coupling and Zeeman operators in the context of quasi-degenerate perturbation theory into the general spin restricted open-shell configuration interaction singles method. The implementation of the mentioned operators allows for the calculation of magnetic circularly polarized dichroism (MCD), L-edge X-ray absorption spectra (XAS) and X-ray magnetic circularly polarized dichroism (XMCD) spectra. The method was tested on calculating the MCD spectra of isostructural complexes [LCr<sup>III</sup>(PyA)<sub>3</sub>Ni<sup>II</sup>]<sup>2+</sup>, [LCr<sup>III</sup>(PyA)<sub>3</sub>Zn<sup>II</sup>]<sup>2+</sup>and [LGa<sup>III</sup>(PyA)<sub>3</sub>Ni<sup>II</sup>]<sup>2+</sup>, with <i>L</i> = 1,4,7-trimethyl-1,4,7-triazacyclonanane and PyA<sup>–</sup> is the monoanion of pyridine-2-aldozime, where it correctly predicts the MCD signs of the lower optical transition of [LCr<sup>III</sup>(PyA)<sub>3</sub>Ni<sup>II</sup>]<sup>2+</sup>and [LGa<sup>III</sup>(PyA)<sub>3</sub>Ni<sup>II</sup>]<sup>2+</sup>. The capabilities of the method in computing L-edge XAS and XMCD spectra were tested on the model complexes [Cu(H<sub>2</sub>O)<sub>6</sub>]<sup>2+</sup> and [Cu<sub>2</sub>(OAc)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>], where it correctly calculates the L<sub>2,3</sub>-edge absorption and XMCD spectra, as well as on the antiferromagnetically coupled Cu–Fe dimer [(F<sub>8</sub>TPP)Fe(μ-O)Cu(TMPA)]<sup>+</sup>, where it correctly predicts the signs of the L<sub>2</sub> and L<sub>3</sub> edges of the Cu XMCD spectrum. To further illustrate the applicability of the method, the more complex L<sub>2,3</sub>-edge XAS and XMCD spectra of thiolate Fe complexes were also calculated.</p>","PeriodicalId":59,"journal":{"name":"The Journal of Physical Chemistry A","volume":"129 40","pages":"9486–9503"},"PeriodicalIF":2.8000,"publicationDate":"2025-09-30","publicationTypes":"Journal Article","fieldsOfStudy":null,"isOpenAccess":false,"openAccessPdf":"https://pubs.acs.org/doi/pdf/10.1021/acs.jpca.5c05086","citationCount":"0","resultStr":"{\"title\":\"General Spin Restricted Open-Shell Configuration Interaction Singles (GS-ROCIS): Implementation of Spin–Orbit Coupling and Zeeman Operators for Calculation of Optical and X-ray Absorption and Magnetic Circular Dichroism Spectra of Magnetically Coupled Transition Metal Systems\",\"authors\":\"Tiago Leyser da Costa Gouveia, , , Lucas Lang, , , Dimitrios Maganas, , and , Frank Neese*, \",\"doi\":\"10.1021/acs.jpca.5c05086\",\"DOIUrl\":null,\"url\":null,\"abstract\":\"<p >In this paper we present the theory and implementation of the spin–orbit coupling and Zeeman operators in the context of quasi-degenerate perturbation theory into the general spin restricted open-shell configuration interaction singles method. The implementation of the mentioned operators allows for the calculation of magnetic circularly polarized dichroism (MCD), L-edge X-ray absorption spectra (XAS) and X-ray magnetic circularly polarized dichroism (XMCD) spectra. The method was tested on calculating the MCD spectra of isostructural complexes [LCr<sup>III</sup>(PyA)<sub>3</sub>Ni<sup>II</sup>]<sup>2+</sup>, [LCr<sup>III</sup>(PyA)<sub>3</sub>Zn<sup>II</sup>]<sup>2+</sup>and [LGa<sup>III</sup>(PyA)<sub>3</sub>Ni<sup>II</sup>]<sup>2+</sup>, with <i>L</i> = 1,4,7-trimethyl-1,4,7-triazacyclonanane and PyA<sup>–</sup> is the monoanion of pyridine-2-aldozime, where it correctly predicts the MCD signs of the lower optical transition of [LCr<sup>III</sup>(PyA)<sub>3</sub>Ni<sup>II</sup>]<sup>2+</sup>and [LGa<sup>III</sup>(PyA)<sub>3</sub>Ni<sup>II</sup>]<sup>2+</sup>. The capabilities of the method in computing L-edge XAS and XMCD spectra were tested on the model complexes [Cu(H<sub>2</sub>O)<sub>6</sub>]<sup>2+</sup> and [Cu<sub>2</sub>(OAc)<sub>4</sub>(H<sub>2</sub>O)<sub>2</sub>], where it correctly calculates the L<sub>2,3</sub>-edge absorption and XMCD spectra, as well as on the antiferromagnetically coupled Cu–Fe dimer [(F<sub>8</sub>TPP)Fe(μ-O)Cu(TMPA)]<sup>+</sup>, where it correctly predicts the signs of the L<sub>2</sub> and L<sub>3</sub> edges of the Cu XMCD spectrum. To further illustrate the applicability of the method, the more complex L<sub>2,3</sub>-edge XAS and XMCD spectra of thiolate Fe complexes were also calculated.</p>\",\"PeriodicalId\":59,\"journal\":{\"name\":\"The Journal of Physical Chemistry A\",\"volume\":\"129 40\",\"pages\":\"9486–9503\"},\"PeriodicalIF\":2.8000,\"publicationDate\":\"2025-09-30\",\"publicationTypes\":\"Journal Article\",\"fieldsOfStudy\":null,\"isOpenAccess\":false,\"openAccessPdf\":\"https://pubs.acs.org/doi/pdf/10.1021/acs.jpca.5c05086\",\"citationCount\":\"0\",\"resultStr\":null,\"platform\":\"Semanticscholar\",\"paperid\":null,\"PeriodicalName\":\"The Journal of Physical Chemistry A\",\"FirstCategoryId\":\"1\",\"ListUrlMain\":\"https://pubs.acs.org/doi/10.1021/acs.jpca.5c05086\",\"RegionNum\":2,\"RegionCategory\":\"化学\",\"ArticlePicture\":[],\"TitleCN\":null,\"AbstractTextCN\":null,\"PMCID\":null,\"EPubDate\":\"\",\"PubModel\":\"\",\"JCR\":\"Q3\",\"JCRName\":\"CHEMISTRY, PHYSICAL\",\"Score\":null,\"Total\":0}","platform":"Semanticscholar","paperid":null,"PeriodicalName":"The Journal of Physical Chemistry A","FirstCategoryId":"1","ListUrlMain":"https://pubs.acs.org/doi/10.1021/acs.jpca.5c05086","RegionNum":2,"RegionCategory":"化学","ArticlePicture":[],"TitleCN":null,"AbstractTextCN":null,"PMCID":null,"EPubDate":"","PubModel":"","JCR":"Q3","JCRName":"CHEMISTRY, PHYSICAL","Score":null,"Total":0}
General Spin Restricted Open-Shell Configuration Interaction Singles (GS-ROCIS): Implementation of Spin–Orbit Coupling and Zeeman Operators for Calculation of Optical and X-ray Absorption and Magnetic Circular Dichroism Spectra of Magnetically Coupled Transition Metal Systems
In this paper we present the theory and implementation of the spin–orbit coupling and Zeeman operators in the context of quasi-degenerate perturbation theory into the general spin restricted open-shell configuration interaction singles method. The implementation of the mentioned operators allows for the calculation of magnetic circularly polarized dichroism (MCD), L-edge X-ray absorption spectra (XAS) and X-ray magnetic circularly polarized dichroism (XMCD) spectra. The method was tested on calculating the MCD spectra of isostructural complexes [LCrIII(PyA)3NiII]2+, [LCrIII(PyA)3ZnII]2+and [LGaIII(PyA)3NiII]2+, with L = 1,4,7-trimethyl-1,4,7-triazacyclonanane and PyA– is the monoanion of pyridine-2-aldozime, where it correctly predicts the MCD signs of the lower optical transition of [LCrIII(PyA)3NiII]2+and [LGaIII(PyA)3NiII]2+. The capabilities of the method in computing L-edge XAS and XMCD spectra were tested on the model complexes [Cu(H2O)6]2+ and [Cu2(OAc)4(H2O)2], where it correctly calculates the L2,3-edge absorption and XMCD spectra, as well as on the antiferromagnetically coupled Cu–Fe dimer [(F8TPP)Fe(μ-O)Cu(TMPA)]+, where it correctly predicts the signs of the L2 and L3 edges of the Cu XMCD spectrum. To further illustrate the applicability of the method, the more complex L2,3-edge XAS and XMCD spectra of thiolate Fe complexes were also calculated.
期刊介绍:
The Journal of Physical Chemistry A is devoted to reporting new and original experimental and theoretical basic research of interest to physical chemists, biophysical chemists, and chemical physicists.