DOI: 10.1063/1.448626. Direct theoretical <i>ab initio</i> calculations in exchange coupled copper(II) dimers: Influence of the choice of the atomic basis set on the singlet–triplet splitting in modeled and real copper dimers

Direct theoretical ab initio calculations in exchange coupled copper(II) dimers: Influence of the choice of the atomic basis set on the singlet–triplet splitting in modeled and real copper dimers

10.1063/1.448626

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

The singlet–triplet splitting (2J=EST) is calculated in bis-[bromo-(N,N-diethylaminoethanolato)copper(II)], belonging to the group of alkoxo-bridged copper(II) dimers, by a recently proposed ab initio method. The singlet–triplet splitting energy is obtained by a perturbation expansion closely related to Anderson’s formalism. The role of all valence electrons is taken into account and it is shown to be very important in order to obtain a satisfying agreement with the experimental result. Two important facts, from a computational point of view, are tested: influence of the atomic basis set size, and influence of modifying of the ligands. Changes in the basis set of the bridging atoms can induce variations in the results from 10% to 20%. As a final result, the theoretical value of the real complex is calculated to 2J(calc)=−1095 cm−1 and agrees with the experimental one 2J(exp)=−817 cm−1.

Bibliography

de Loth, P., Daudey, J.-P., Astheimer, H., Walz, L., & Haase, W. (1985). Direct theoretical ab initio calculations in exchange coupled copper(II) dimers: Influence of the choice of the atomic basis set on the singletâtriplet splitting in modeled and real copper dimers. The Journal of Chemical Physics, 82(11), 5048â5052.

Authors 5

Philippe de Loth (first)
Jean-Pierre Daudey (additional)
Harald Astheimer (additional)
Leonhard Walz (additional)
Wolfgang Haase (additional)

References 24 Referenced 36

10.1021/ja00404a007 / J. Am. Chem. Soc. (1981)
{'key': '2024021002062262800_r2'}
10.1021/ja00521a020 / J. Am. Chem. Soc. (1980)
{'key': '2024021002062262800_r4'}
10.1016/S0081-1947(08)60260-X / Solid State Phys. (1963)
{'key': '2024021002062262800_r6', 'first-page': '4855', 'volume': '47', 'year': '1967', 'journal-title': 'J. Chem. Phys.'} / J. Chem. Phys. (1967)
10.1021/ic00191a027 / Inorg. Chem. (1984)
{'key': '2024021002062262800_r8'}
{'key': '2024021002062262800_r9', 'first-page': '269', 'volume': '72', 'year': '1976', 'journal-title': 'J. Chem. Soc. Faraday Trans. 2'} / J. Chem. Soc. Faraday Trans. 2 (1976)
{'key': '2024021002062262800_r10', 'first-page': '531', 'volume': '82', 'year': '1981', 'journal-title': 'Chem. Phys. Lett.'} / Chem. Phys. Lett. (1981)
10.1021/ja00850a018 / J. Am. Chem. Soc. (1975)
{'key': '2024021002062262800_r12', 'first-page': '1', 'volume': '24', 'year': '1976', 'journal-title': 'Phys. Rev.'} / Phys. Rev. (1976)
10.1080/00018737700101443 / Adv. Phys. (1977)
{'key': '2024021002062262800_r14'}
{'key': '2024021002062262800_r15'}
{'key': '2024021002062262800_r16'}
{'key': '2024021002062262800_r17', 'first-page': '200', 'volume': '44', 'year': '1971', 'journal-title': 'Suomen Kemistilehti B'} / Suomen Kemistilehti B (1971)
10.1002/cber.19731061006 / Chem. Ber. (1973)
10.1002/zaac.19683600107 / Z. Anorg. Allg. Chem. (1968)
{'key': '2024021002062262800_r20'}
{'key': '2024021002062262800_r21'}
{'key': '2024021002062262800_r22'}
{'key': '2024021002062262800_r23', 'first-page': '255', 'volume': '108', 'year': '1978', 'journal-title': 'Gazz. Chim. Ital.'} / Gazz. Chim. Ital. (1978)
10.1063/1.442119 / J. Chem. Phys. (1981)

Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 9:08 a.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 10:22 p.m.)
Indexed	11 months ago (Oct. 5, 2024, 8:28 p.m.)
Issued	40 years, 3 months ago (June 1, 1985)
Published	40 years, 3 months ago (June 1, 1985)
Published Print	40 years, 3 months ago (June 1, 1985)

Funders 0

None

BibTeX

@article{de_Loth_1985, title={Direct theoretical ab initio calculations in exchange coupled copper(II) dimers: Influence of the choice of the atomic basis set on the singlet–triplet splitting in modeled and real copper dimers}, volume={82}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.448626}, DOI={10.1063/1.448626}, number={11}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={de Loth, Philippe and Daudey, Jean-Pierre and Astheimer, Harald and Walz, Leonhard and Haase, Wolfgang}, year={1985}, month=jun, pages={5048–5052} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2024,
        10,
        6
      ]
    ],
    "date-time": "2024-10-06T00:28:35Z",
    "timestamp": 1728174515476
  },
  "reference-count": 24,
  "publisher": "AIP Publishing",
  "issue": "11",
  "content-domain": {
    "domain": [
      "pubs.aip.org"
    ],
    "crossmark-restriction": true
  },
  "published-print": {
    "date-parts": [
      [
        1985,
        6,
        1
      ]
    ]
  },
  "abstract": "<jats:p>The singlet\u2013triplet splitting (2J=EST) is calculated in bis-[bromo-(N,N-diethylaminoethanolato)copper(II)], belonging to the group of alkoxo-bridged copper(II) dimers, by a recently proposed ab initio method. The singlet\u2013triplet splitting energy is obtained by a perturbation expansion closely related to Anderson\u2019s formalism. The role of all valence electrons is taken into account and it is shown to be very important in order to obtain a satisfying agreement with the experimental result. Two important facts, from a computational point of view, are tested: influence of the atomic basis set size, and influence of modifying of the ligands. Changes in the basis set of the bridging atoms can induce variations in the results from 10% to 20%. As a final result, the theoretical value of the real complex is calculated to 2J(calc)=\u22121095 cm\u22121 and agrees with the experimental one 2J(exp)=\u2212817 cm\u22121.</jats:p>",
  "DOI": "10.1063/1.448626",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2002,
        7,
        26
      ]
    ],
    "date-time": "2002-07-26T13:08:03Z",
    "timestamp": 1027688883000
  },
  "page": "5048-5052",
  "update-policy": "http://dx.doi.org/10.1063/aip-crossmark-policy-page",
  "source": "Crossref",
  "is-referenced-by-count": 36,
  "title": "Direct theoretical <i>ab initio</i> calculations in exchange coupled copper(II) dimers: Influence of the choice of the atomic basis set on the singlet\u2013triplet splitting in modeled and real copper dimers",
  "prefix": "10.1063",
  "volume": "82",
  "author": [
    {
      "given": "Philippe",
      "family": "de Loth",
      "sequence": "first",
      "affiliation": [
        {
          "name": "Laboratoire de Chimie de Coordination du CNRS, associ\u00e9 \u00e0 l\u2019Universit\u00e9 Paul Sabatier, 205 route de Narbonne, 31400 Toulouse, France"
        }
      ]
    },
    {
      "given": "Jean-Pierre",
      "family": "Daudey",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Laboratoire de Physique Quantique (ERA 821 CNRS), Universit\u00e9 Paul Sabatier, 118 route de Narbonne, 31400 Toulouse, France"
        }
      ]
    },
    {
      "given": "Harald",
      "family": "Astheimer",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Institut fuer Physikalische Chemie, Technische Hochschule Darmstadt, Petersenstrasse 20, D 6100 Darmstadt, West Germany"
        }
      ]
    },
    {
      "given": "Leonhard",
      "family": "Walz",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Institut fuer Physikalische Chemie, Technische Hochschule Darmstadt, Petersenstrasse 20, D 6100 Darmstadt, West Germany"
        }
      ]
    },
    {
      "given": "Wolfgang",
      "family": "Haase",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Institut fuer Physikalische Chemie, Technische Hochschule Darmstadt, Petersenstrasse 20, D 6100 Darmstadt, West Germany"
        }
      ]
    }
  ],
  "member": "317",
  "reference": [
    {
      "key": "2024021002062262800_r1",
      "doi-asserted-by": "crossref",
      "first-page": "4007",
      "DOI": "10.1021/ja00404a007",
      "volume": "103",
      "year": "1981",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "2024021002062262800_r2"
    },
    {
      "key": "2024021002062262800_r3",
      "doi-asserted-by": "crossref",
      "first-page": "111",
      "DOI": "10.1021/ja00521a020",
      "volume": "102",
      "year": "1980",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "2024021002062262800_r4"
    },
    {
      "key": "2024021002062262800_r5",
      "doi-asserted-by": "crossref",
      "first-page": "99",
      "DOI": "10.1016/S0081-1947(08)60260-X",
      "volume": "14",
      "year": "1963",
      "journal-title": "Solid State Phys."
    },
    {
      "key": "2024021002062262800_r6",
      "first-page": "4855",
      "volume": "47",
      "year": "1967",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002062262800_r7",
      "doi-asserted-by": "crossref",
      "first-page": "3802",
      "DOI": "10.1021/ic00191a027",
      "volume": "23",
      "year": "1984",
      "journal-title": "Inorg. Chem."
    },
    {
      "key": "2024021002062262800_r8"
    },
    {
      "key": "2024021002062262800_r9",
      "first-page": "269",
      "volume": "72",
      "year": "1976",
      "journal-title": "J. Chem. Soc. Faraday Trans. 2"
    },
    {
      "key": "2024021002062262800_r10",
      "first-page": "531",
      "volume": "82",
      "year": "1981",
      "journal-title": "Chem. Phys. Lett."
    },
    {
      "key": "2024021002062262800_r11",
      "doi-asserted-by": "crossref",
      "first-page": "4884",
      "DOI": "10.1021/ja00850a018",
      "volume": "97",
      "year": "1975",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "2024021002062262800_r12",
      "first-page": "1",
      "volume": "24",
      "year": "1976",
      "journal-title": "Phys. Rev."
    },
    {
      "key": "2024021002062262800_r13",
      "doi-asserted-by": "crossref",
      "first-page": "651",
      "DOI": "10.1080/00018737700101443",
      "volume": "26",
      "year": "1977",
      "journal-title": "Adv. Phys."
    },
    {
      "key": "2024021002062262800_r14"
    },
    {
      "key": "2024021002062262800_r15"
    },
    {
      "key": "2024021002062262800_r16"
    },
    {
      "key": "2024021002062262800_r17",
      "first-page": "200",
      "volume": "44",
      "year": "1971",
      "journal-title": "Suomen Kemistilehti B"
    },
    {
      "key": "2024021002062262800_r18",
      "doi-asserted-by": "crossref",
      "first-page": "3132",
      "DOI": "10.1002/cber.19731061006",
      "volume": "106",
      "year": "1973",
      "journal-title": "Chem. Ber."
    },
    {
      "key": "2024021002062262800_r19",
      "doi-asserted-by": "crossref",
      "first-page": "39",
      "DOI": "10.1002/zaac.19683600107",
      "volume": "360",
      "year": "1968",
      "journal-title": "Z. Anorg. Allg. Chem."
    },
    {
      "key": "2024021002062262800_r20"
    },
    {
      "key": "2024021002062262800_r21"
    },
    {
      "key": "2024021002062262800_r22"
    },
    {
      "key": "2024021002062262800_r23",
      "first-page": "255",
      "volume": "108",
      "year": "1978",
      "journal-title": "Gazz. Chim. Ital."
    },
    {
      "key": "2024021002062262800_r24",
      "doi-asserted-by": "crossref",
      "first-page": "775",
      "DOI": "10.1063/1.442119",
      "volume": "75",
      "year": "1981",
      "journal-title": "J. Chem. Phys."
    }
  ],
  "container-title": "The Journal of Chemical Physics",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://pubs.aip.org/aip/jcp/article-pdf/82/11/5048/18953531/5048_1_online.pdf",
      "content-type": "application/pdf",
      "content-version": "vor",
      "intended-application": "syndication"
    },
    {
      "URL": "https://pubs.aip.org/aip/jcp/article-pdf/82/11/5048/18953531/5048_1_online.pdf",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2024,
        2,
        10
      ]
    ],
    "date-time": "2024-02-10T03:22:09Z",
    "timestamp": 1707535329000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://pubs.aip.org/jcp/article/82/11/5048/609504/Direct-theoretical-ab-initio-calculations-in"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        1985,
        6,
        1
      ]
    ]
  },
  "references-count": 24,
  "journal-issue": {
    "issue": "11",
    "published-print": {
      "date-parts": [
        [
          1985,
          6,
          1
        ]
      ]
    }
  },
  "URL": "http://dx.doi.org/10.1063/1.448626",
  "relation": {},
  "ISSN": [
    "0021-9606",
    "1089-7690"
  ],
  "subject": [],
  "published-other": {
    "date-parts": [
      [
        1985,
        6,
        1
      ]
    ]
  },
  "published": {
    "date-parts": [
      [
        1985,
        6,
        1
      ]
    ]
  }
}