DOI: 10.1063/1.448837. Spin density of radicals by finite field many-body methods

Spin density of radicals by finite field many-body methods

10.1063/1.448837

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

The spin densities of several small radicals CH3, NH2,CH2CH, BeH, and H2CO+ are calculated by a finite field coupled-cluster method using a spin density operator as a finite perturbation on the systems. The calculated hyperfine coupling constants of the π radicals are in good agreement with experiment at a low level of correlation. The CH2CH radical required a higher level of correlation to obtain the experimental value. The calculations are also performed for the H2CO+ radical where theory has failed to predict the experimental splitting constants. The spin density on hydrogen calculated in the present study is lower than the result obtained by the low temperature gas ESR techniques, although the carbon spin density is well reproduced. An analysis of possible corrections for the H spin density is presented.

Bibliography

Sekino, H., & Bartlett, R. J. (1985). Spin density of radicals by finite field many-body methods. The Journal of Chemical Physics, 82(9), 4225â4229.

Authors 2

Hideo Sekino (first)
Rodney J. Bartlett (additional)

References 38 Referenced 118

10.1063/1.438364 / J. Chem. Phys. (1979)
10.1063/1.1673213 / J. Chem. Phys. (1970)
10.1063/1.1672830 / J. Chem. Phys. (1970)
10.1063/1.1675476 / J. Chem. Phys. (1971)
10.1021/j100691a002 / J. Phys. Chem. (1971)
10.1021/ja00771a013 / J. Am. Chem. Soc. (1972)
10.1063/1.430262 / J. Chem. Phys. (1975)
10.1063/1.430252 / J. Chem. Phys. (1975)
10.1021/ja00484a006 / J. Am. Chem. Soc. (1978)
10.1063/1.442767 / J. Chem. Phys. (1982)
10.1063/1.441667 / J. Chem. Phys. (1981)
10.1063/1.446543 / J. Chem. Phys. (1984)
10.1063/1.446826 / J. Chem. Phys. (1984)
10.1063/1.440313 / J. Chem. Phys. (1980)
10.1021/j100239a022 / J. Phys. Chem. (1983)
10.1103/PhysRevA.20.1313 / Phys. Rev. A (1979)
10.1063/1.1670536 / J. Chem. Phys. (1968)
10.1146/annurev.pc.32.100181.002043 / Annu. Rev. Phys. Chem. (1981)
10.1063/1.443164 / J. Chem. Phys. (1982)
{'key': '2024021002031610000_r8'}
{'key': '2024021002031610000_r8a'}
{'key': '2024021002031610000_r9', 'first-page': '67', 'volume': '2', 'year': '1968', 'journal-title': 'Int. J. Quantum Chem. Symp.'} / Int. J. Quantum Chem. Symp. (1968)
10.1002/qua.560060112 / Int. J. Quantum Chem. (1972)
10.1063/1.1674408 / J. Chem. Phys. (1970)
10.1021/ja00505a009 / Am. Chem. Soc. (1979)
10.1063/1.445226 / J. Chem. Phys. (1983)
10.1063/1.1671609 / J. Chem. Phys. (1969)
10.1063/1.441784 / J. Chem. Phys. (1981)
{'key': '2024021002031610000_r15'}
{'key': '2024021002031610000_r16', 'first-page': '255', 'volume': '18', 'year': '1984', 'journal-title': 'Int. J. Quantum Chem. Symp.'} / Int. J. Quantum Chem. Symp. (1984)
10.1103/PhysRevLett.1.91 / Phys. Rev. Lett. (1958)
10.1063/1.1677336 / J. Chem. Phys. (1972)
{'key': '2024021002031610000_r19', 'first-page': '79', 'volume': '71', 'year': '1967', 'journal-title': 'J. Phys. Chem.'} / J. Phys. Chem. (1967)
10.1063/1.1701415 / J. Chem. Phys. (1963)
{'key': '2024021002031610000_r20'}
10.1063/1.446827 / J. Chem. Phys. (1984)
{'key': '2024021002031610000_r22'}
10.1016/0022-2860(80)80354-1 / J. Mol. Struct. (1980)

Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 9 a.m.)
Deposited	1 year, 6 months ago (Feb. 9, 2024, 10:17 p.m.)
Indexed	1 week, 1 day ago (Aug. 29, 2025, 5:42 a.m.)
Issued	40 years, 4 months ago (May 1, 1985)
Published	40 years, 4 months ago (May 1, 1985)
Published Print	40 years, 4 months ago (May 1, 1985)

Funders 0

None

BibTeX

@article{Sekino_1985, title={Spin density of radicals by finite field many-body methods}, volume={82}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.448837}, DOI={10.1063/1.448837}, number={9}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Sekino, Hideo and Bartlett, Rodney J.}, year={1985}, month=may, pages={4225–4229} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2025,
        8,
        29
      ]
    ],
    "date-time": "2025-08-29T09:42:59Z",
    "timestamp": 1756460579261
  },
  "reference-count": 38,
  "publisher": "AIP Publishing",
  "issue": "9",
  "content-domain": {
    "domain": [
      "pubs.aip.org"
    ],
    "crossmark-restriction": true
  },
  "published-print": {
    "date-parts": [
      [
        1985,
        5,
        1
      ]
    ]
  },
  "abstract": "<jats:p>The spin densities of several small radicals CH3, NH2,CH2CH, BeH, and H2CO+ are calculated by a finite field coupled-cluster method using a spin density operator as a finite perturbation on the systems. The calculated hyperfine coupling constants of the \u03c0 radicals are in good agreement with experiment at a low level of correlation. The CH2CH radical required a higher level of correlation to obtain the experimental value. The calculations are also performed for the H2CO+ radical where theory has failed to predict the experimental splitting constants. The spin density on hydrogen calculated in the present study is lower than the result obtained by the low temperature gas ESR techniques, although the carbon spin density is well reproduced. An analysis of possible corrections for the H spin density is presented.</jats:p>",
  "DOI": "10.1063/1.448837",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2002,
        7,
        26
      ]
    ],
    "date-time": "2002-07-26T13:00:36Z",
    "timestamp": 1027688436000
  },
  "page": "4225-4229",
  "update-policy": "http://dx.doi.org/10.1063/aip-crossmark-policy-page",
  "source": "Crossref",
  "is-referenced-by-count": 118,
  "title": "Spin density of radicals by finite field many-body methods",
  "prefix": "10.1063",
  "volume": "82",
  "author": [
    {
      "given": "Hideo",
      "family": "Sekino",
      "sequence": "first",
      "affiliation": [
        {
          "name": "Quantum Theory Project, University of Florida, Gainesville, Florida 32611"
        }
      ]
    },
    {
      "given": "Rodney J.",
      "family": "Bartlett",
      "sequence": "additional",
      "affiliation": [
        {
          "name": "Quantum Theory Project, University of Florida, Gainesville, Florida 32611"
        }
      ]
    }
  ],
  "member": "317",
  "reference": [
    {
      "key": "2024021002031610000_r1",
      "doi-asserted-by": "crossref",
      "first-page": "761",
      "DOI": "10.1063/1.438364",
      "volume": "71",
      "year": "1979",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r2",
      "doi-asserted-by": "crossref",
      "first-page": "1740",
      "DOI": "10.1063/1.1673213",
      "volume": "52",
      "year": "1970",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r2a",
      "doi-asserted-by": "crossref",
      "first-page": "5596",
      "DOI": "10.1063/1.1672830",
      "volume": "52",
      "year": "1970",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r2b",
      "doi-asserted-by": "crossref",
      "first-page": "4121",
      "DOI": "10.1063/1.1675476",
      "volume": "54",
      "year": "1971",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r2c",
      "doi-asserted-by": "crossref",
      "first-page": "3400",
      "DOI": "10.1021/j100691a002",
      "volume": "75",
      "year": "1971",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024021002031610000_r2d",
      "doi-asserted-by": "crossref",
      "first-page": "5603",
      "DOI": "10.1021/ja00771a013",
      "volume": "94",
      "year": "1972",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "2024021002031610000_r2e",
      "doi-asserted-by": "crossref",
      "first-page": "1",
      "DOI": "10.1063/1.430262",
      "volume": "62",
      "year": "1975",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r2f",
      "doi-asserted-by": "crossref",
      "first-page": "10",
      "DOI": "10.1063/1.430252",
      "volume": "62",
      "year": "1975",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r2g",
      "doi-asserted-by": "crossref",
      "first-page": "4961",
      "DOI": "10.1021/ja00484a006",
      "volume": "100",
      "year": "1978",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "2024021002031610000_r3",
      "doi-asserted-by": "crossref",
      "first-page": "126",
      "DOI": "10.1063/1.442767",
      "volume": "76",
      "year": "1982",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r3a",
      "doi-asserted-by": "crossref",
      "first-page": "4256",
      "DOI": "10.1063/1.441667",
      "volume": "74",
      "year": "1981",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r3b",
      "doi-asserted-by": "crossref",
      "first-page": "4593",
      "DOI": "10.1063/1.446543",
      "volume": "80",
      "year": "1984",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r3c",
      "doi-asserted-by": "crossref",
      "first-page": "1006",
      "DOI": "10.1063/1.446826",
      "volume": "80",
      "year": "1984",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r4",
      "doi-asserted-by": "crossref",
      "first-page": "1770",
      "DOI": "10.1063/1.440313",
      "volume": "73",
      "year": "1980",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r4a",
      "doi-asserted-by": "crossref",
      "first-page": "3068",
      "DOI": "10.1021/j100239a022",
      "volume": "87",
      "year": "1983",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024021002031610000_r5",
      "doi-asserted-by": "crossref",
      "first-page": "1313",
      "DOI": "10.1103/PhysRevA.20.1313",
      "volume": "20",
      "year": "1979",
      "journal-title": "Phys. Rev. A"
    },
    {
      "key": "2024021002031610000_r5a",
      "doi-asserted-by": "crossref",
      "first-page": "2960",
      "DOI": "10.1063/1.1670536",
      "volume": "49",
      "year": "1968",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r6",
      "doi-asserted-by": "crossref",
      "first-page": "359",
      "DOI": "10.1146/annurev.pc.32.100181.002043",
      "volume": "32",
      "year": "1981",
      "journal-title": "Annu. Rev. Phys. Chem."
    },
    {
      "key": "2024021002031610000_r7",
      "doi-asserted-by": "crossref",
      "first-page": "1910",
      "DOI": "10.1063/1.443164",
      "volume": "76",
      "year": "1982",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r8"
    },
    {
      "key": "2024021002031610000_r8a"
    },
    {
      "key": "2024021002031610000_r9",
      "first-page": "67",
      "volume": "2",
      "year": "1968",
      "journal-title": "Int. J. Quantum Chem. Symp."
    },
    {
      "key": "2024021002031610000_r9a",
      "doi-asserted-by": "crossref",
      "first-page": "155",
      "DOI": "10.1002/qua.560060112",
      "volume": "6",
      "year": "1972",
      "journal-title": "Int. J. Quantum Chem."
    },
    {
      "key": "2024021002031610000_r10",
      "doi-asserted-by": "crossref",
      "first-page": "2823",
      "DOI": "10.1063/1.1674408",
      "volume": "53",
      "year": "1970",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r11",
      "doi-asserted-by": "crossref",
      "first-page": "2856",
      "DOI": "10.1021/ja00505a009",
      "volume": "101",
      "year": "1979",
      "journal-title": "Am. Chem. Soc."
    },
    {
      "key": "2024021002031610000_r12",
      "doi-asserted-by": "crossref",
      "first-page": "3112",
      "DOI": "10.1063/1.445226",
      "volume": "78",
      "year": "1983",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r13",
      "doi-asserted-by": "crossref",
      "first-page": "3649",
      "DOI": "10.1063/1.1671609",
      "volume": "50",
      "year": "1969",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r14",
      "doi-asserted-by": "crossref",
      "first-page": "320",
      "DOI": "10.1063/1.441784",
      "volume": "75",
      "year": "1981",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r15"
    },
    {
      "key": "2024021002031610000_r16",
      "first-page": "255",
      "volume": "18",
      "year": "1984",
      "journal-title": "Int. J. Quantum Chem. Symp."
    },
    {
      "key": "2024021002031610000_r17",
      "doi-asserted-by": "crossref",
      "first-page": "91",
      "DOI": "10.1103/PhysRevLett.1.91",
      "volume": "1",
      "year": "1958",
      "journal-title": "Phys. Rev. Lett."
    },
    {
      "key": "2024021002031610000_r18",
      "doi-asserted-by": "crossref",
      "first-page": "1152",
      "DOI": "10.1063/1.1677336",
      "volume": "56",
      "year": "1972",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r19",
      "first-page": "79",
      "volume": "71",
      "year": "1967",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024021002031610000_r19a",
      "doi-asserted-by": "crossref",
      "first-page": "2147",
      "DOI": "10.1063/1.1701415",
      "volume": "39",
      "year": "1963",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r20"
    },
    {
      "key": "2024021002031610000_r21",
      "doi-asserted-by": "crossref",
      "first-page": "1018",
      "DOI": "10.1063/1.446827",
      "volume": "80",
      "year": "1984",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021002031610000_r22"
    },
    {
      "key": "2024021002031610000_r23",
      "doi-asserted-by": "crossref",
      "first-page": "101",
      "DOI": "10.1016/0022-2860(80)80354-1",
      "volume": "67",
      "year": "1980",
      "journal-title": "J. Mol. Struct."
    }
  ],
  "container-title": "The Journal of Chemical Physics",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://pubs.aip.org/aip/jcp/article-pdf/82/9/4225/18953031/4225_1_online.pdf",
      "content-type": "application/pdf",
      "content-version": "vor",
      "intended-application": "syndication"
    },
    {
      "URL": "https://pubs.aip.org/aip/jcp/article-pdf/82/9/4225/18953031/4225_1_online.pdf",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2024,
        2,
        10
      ]
    ],
    "date-time": "2024-02-10T03:17:55Z",
    "timestamp": 1707535075000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://pubs.aip.org/jcp/article/82/9/4225/88592/Spin-density-of-radicals-by-finite-field-many-body"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        1985,
        5,
        1
      ]
    ]
  },
  "references-count": 38,
  "journal-issue": {
    "issue": "9",
    "published-print": {
      "date-parts": [
        [
          1985,
          5,
          1
        ]
      ]
    }
  },
  "URL": "http://dx.doi.org/10.1063/1.448837",
  "relation": {},
  "ISSN": [
    "0021-9606",
    "1089-7690"
  ],
  "subject": [],
  "published-other": {
    "date-parts": [
      [
        1985,
        5,
        1
      ]
    ]
  },
  "published": {
    "date-parts": [
      [
        1985,
        5,
        1
      ]
    ]
  }
}