DOI: 10.1063/1.1744189. Role of Atomic Valence States in Molecular Energy Calculations

Role of Atomic Valence States in Molecular Energy Calculations

10.1063/1.1744189

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

Ab initio calculations of molecular binding energies are examined critically in a basis of antisymmetrized products of approximate atomic state functions (the approximate composite functions of Moffitt). It is shown that much more accurate results may be expected if the binding energy is calculated relative to a suitably defined generalized valence state V of the dissociation products. The energy of this state V relative to the ground state of the dissociation products is estimated from atomic spectral data. This procedure leads directly to the intra-atomic correlation correction previously proposed by the author as a necessary modification of Moffitt's method of atoms in molecules. Detailed calculations are carried out for the ground states of the molecules LiH and BH, and for the ground and excited states of the benzene molecule (in the usual π-electron approximation). In each case the intra-atomic correlation correction leads to a substantial improvement in the accuracy of the results.

Bibliography

Hurley, A. C. (1958). Role of Atomic Valence States in Molecular Energy Calculations. The Journal of Chemical Physics, 28(4), 532â542.

Authors 1

A. C. Hurley (first)

References 44 Referenced 34

{'key': '2024020817502084200_r1', 'first-page': '245', 'volume': 'A210', 'year': '1951', 'journal-title': 'Proc. Roy. Soc. (London)'} / Proc. Roy. Soc. (London) (1951)
{'key': '2024020817502084200_r2', 'first-page': '49', 'volume': 'A69', 'year': '1956', 'journal-title': 'Proc. Phys. Soc. (London)'} / Proc. Phys. Soc. (London) (1956)
10.1063/1.1743324 / J. Chem. Phys. (1957)
10.1088/0034-4885/17/1/306 / Repts. Progr. in Phys. (1954)
{'key': '2024020817502084200_r5', 'first-page': '90', 'volume': 'A165', 'year': '1938', 'journal-title': 'Proc. Roy. Soc. (London)'} / Proc. Roy. Soc. (London) (1938)
{'key': '2024020817502084200_r6', 'first-page': '868', 'volume': 'A69', 'year': '1956', 'journal-title': 'Proc. Phys. Soc. (London)'} / Proc. Phys. Soc. (London) (1956)
10.1103/PhysRev.36.57 / Phys. Rev. (1930)
{'key': '2024020817502084200_r8', 'first-page': '556', 'volume': '50', 'year': '1953', 'journal-title': 'J. Chem. Phys.'} / J. Chem. Phys. (1953)
{'key': '2024020817502084200_r9', 'first-page': '181', 'volume': 'A114', 'year': '1927', 'journal-title': 'Proc. Roy. Soc. (London)'} / Proc. Roy. Soc. (London) (1927)
{'key': '2024020817502084200_r10', 'first-page': '179', 'volume': 'A226', 'year': '1954', 'journal-title': 'Proc. Roy. Soc. (London)'} / Proc. Roy. Soc. (London) (1954)
10.1063/1.1740588 / J. Chem. Phys. (1955)
{'key': '2024020817502084200_r12', 'first-page': '196', 'volume': 'A201', 'year': '1950', 'journal-title': 'Proc. Roy. Soc. (London)'} / Proc. Roy. Soc. (London) (1950)
{'key': '2024020817502084200_r13', 'first-page': '486', 'volume': 'A218', 'year': '1953', 'journal-title': 'Proc. Roy. Soc. (London)'} / Proc. Roy. Soc. (London) (1953)
{'key': '2024020817502084200_r14', 'first-page': '464', 'volume': 'A218', 'year': '1953', 'journal-title': 'Proc. Roy. Soc. (London)'} / Proc. Roy. Soc. (London) (1953)
{'key': '2024020817502084200_r14a', 'first-page': '530', 'volume': 'A220', 'year': '1953', 'journal-title': 'Proc. R. Soc. London, Ser. A'} / Proc. R. Soc. London, Ser. A (1953)
{'key': '2024020817502084200_r15', 'first-page': '149', 'volume': 'A68', 'year': '1955', 'journal-title': 'Proc. Phys. Soc. (London)'} / Proc. Phys. Soc. (London) (1955)
{'key': '2024020817502084200_r15a', 'first-page': '30', 'volume': '69', 'year': '1956', 'journal-title': 'Proc. Phys. Soc. London'} / Proc. Phys. Soc. London (1956)
10.1088/0370-1298/69/10/306 / Proc. Phys. Soc. London (1956)
{'key': '2024020817502084200_r16'}
{'key': '2024020817502084200_r16a'}
10.1063/1.1749252 / J. Chem. Phys. (1933)
10.1063/1.1700818 / J. Chem. Phys. (1956)
{'key': '2024020817502084200_r19', 'first-page': '237', 'volume': '4', 'year': '1954', 'journal-title': 'Acta. Phys. Acad. Sci. Hung.'} / Acta. Phys. Acad. Sci. Hung. (1954)
{'key': '2024020817502084200_r20'}
10.1063/1.1749394 / J. Chem. Phys. (1934)
10.1039/tf9534901254 / Trans. Faraday Soc. (1953)
10.1103/PhysRev.97.1474 / Phys. Rev. (1955)
{'key': '2024020817502084200_r25', 'first-page': '349', 'volume': '5', 'year': '1952', 'journal-title': 'Arkiv Fysik'} / Arkiv Fysik (1952)
{'key': '2024020817502084200_r26'}
10.1063/1.1743266 / J. Chem. Phys. (1957)
10.1063/1.1743477 / J. Chem. Phys. (1957)
{'key': '2024020817502084200_r29'}
{'key': '2024020817502084200_r29a'}
{'key': '2024020817502084200_r30'}
{'key': '2024020817502084200_r30a'}
{'key': '2024020817502084200_r31'}
{'key': '2024020817502084200_r32'}
10.1063/1.1742881 / J. Chem. Phys. (1956)
{'key': '2024020817502084200_r34'}
{'key': '2024020817502084200_r35'}
10.1103/RevModPhys.23.69 / Revs. Modern Phys. (1951)
{'key': '2024020817502084200_r37', 'first-page': '1094', 'volume': '239', 'year': '1955', 'journal-title': 'Compt. Rend.'} / Compt. Rend. (1955)
{'key': '2024020817502084200_r38'}
10.1063/1.1747540 / J. Chem. Phys. (1950)

Dates

Type	When
Created	20 years, 8 months ago (Jan. 5, 2005, 9:04 p.m.)
Deposited	1 year, 6 months ago (Feb. 8, 2024, 1:38 p.m.)
Indexed	1 year, 6 months ago (Feb. 9, 2024, 12:30 a.m.)
Issued	67 years, 5 months ago (April 1, 1958)
Published	67 years, 5 months ago (April 1, 1958)
Published Print	67 years, 5 months ago (April 1, 1958)

Funders 0

None

BibTeX

@article{Hurley_1958, title={Role of Atomic Valence States in Molecular Energy Calculations}, volume={28}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.1744189}, DOI={10.1063/1.1744189}, number={4}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Hurley, A. C.}, year={1958}, month=apr, pages={532–542} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2024,
        2,
        9
      ]
    ],
    "date-time": "2024-02-09T05:30:35Z",
    "timestamp": 1707456635895
  },
  "reference-count": 44,
  "publisher": "AIP Publishing",
  "issue": "4",
  "content-domain": {
    "domain": [
      "pubs.aip.org"
    ],
    "crossmark-restriction": true
  },
  "published-print": {
    "date-parts": [
      [
        1958,
        4,
        1
      ]
    ]
  },
  "abstract": "<jats:p>Ab initio calculations of molecular binding energies are examined critically in a basis of antisymmetrized products of approximate atomic state functions (the approximate composite functions of Moffitt). It is shown that much more accurate results may be expected if the binding energy is calculated relative to a suitably defined generalized valence state V of the dissociation products. The energy of this state V relative to the ground state of the dissociation products is estimated from atomic spectral data. This procedure leads directly to the intra-atomic correlation correction previously proposed by the author as a necessary modification of Moffitt's method of atoms in molecules.</jats:p>\n               <jats:p>Detailed calculations are carried out for the ground states of the molecules LiH and BH, and for the ground and excited states of the benzene molecule (in the usual \u03c0-electron approximation). In each case the intra-atomic correlation correction leads to a substantial improvement in the accuracy of the results.</jats:p>",
  "DOI": "10.1063/1.1744189",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2005,
        1,
        6
      ]
    ],
    "date-time": "2005-01-06T02:04:38Z",
    "timestamp": 1104977078000
  },
  "page": "532-542",
  "update-policy": "http://dx.doi.org/10.1063/aip-crossmark-policy-page",
  "source": "Crossref",
  "is-referenced-by-count": 34,
  "title": "Role of Atomic Valence States in Molecular Energy Calculations",
  "prefix": "10.1063",
  "volume": "28",
  "author": [
    {
      "given": "A. C.",
      "family": "Hurley",
      "sequence": "first",
      "affiliation": [
        {
          "name": "Solid-State and Molecular Theory Group, Massachusetts Institute of Technology, Cambridge, Massachusetts"
        }
      ]
    }
  ],
  "member": "317",
  "reference": [
    {
      "key": "2024020817502084200_r1",
      "first-page": "245",
      "volume": "A210",
      "year": "1951",
      "journal-title": "Proc. Roy. Soc. (London)"
    },
    {
      "key": "2024020817502084200_r2",
      "first-page": "49",
      "volume": "A69",
      "year": "1956",
      "journal-title": "Proc. Phys. Soc. (London)"
    },
    {
      "key": "2024020817502084200_r3",
      "doi-asserted-by": "crossref",
      "first-page": "435",
      "DOI": "10.1063/1.1743324",
      "volume": "26",
      "year": "1957",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020817502084200_r4",
      "doi-asserted-by": "crossref",
      "first-page": "173",
      "DOI": "10.1088/0034-4885/17/1/306",
      "volume": "17",
      "year": "1954",
      "journal-title": "Repts. Progr. in Phys."
    },
    {
      "key": "2024020817502084200_r5",
      "first-page": "90",
      "volume": "A165",
      "year": "1938",
      "journal-title": "Proc. Roy. Soc. (London)"
    },
    {
      "key": "2024020817502084200_r6",
      "first-page": "868",
      "volume": "A69",
      "year": "1956",
      "journal-title": "Proc. Phys. Soc. (London)"
    },
    {
      "key": "2024020817502084200_r7",
      "doi-asserted-by": "crossref",
      "first-page": "57",
      "DOI": "10.1103/PhysRev.36.57",
      "volume": "36",
      "year": "1930",
      "journal-title": "Phys. Rev."
    },
    {
      "key": "2024020817502084200_r8",
      "first-page": "556",
      "volume": "50",
      "year": "1953",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020817502084200_r9",
      "first-page": "181",
      "volume": "A114",
      "year": "1927",
      "journal-title": "Proc. Roy. Soc. (London)"
    },
    {
      "key": "2024020817502084200_r10",
      "first-page": "179",
      "volume": "A226",
      "year": "1954",
      "journal-title": "Proc. Roy. Soc. (London)"
    },
    {
      "key": "2024020817502084200_r11",
      "doi-asserted-by": "crossref",
      "first-page": "1833",
      "DOI": "10.1063/1.1740588",
      "volume": "23",
      "year": "1955",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020817502084200_r12",
      "first-page": "196",
      "volume": "A201",
      "year": "1950",
      "journal-title": "Proc. Roy. Soc. (London)"
    },
    {
      "key": "2024020817502084200_r13",
      "first-page": "486",
      "volume": "A218",
      "year": "1953",
      "journal-title": "Proc. Roy. Soc. (London)"
    },
    {
      "key": "2024020817502084200_r14",
      "first-page": "464",
      "volume": "A218",
      "year": "1953",
      "journal-title": "Proc. Roy. Soc. (London)"
    },
    {
      "key": "2024020817502084200_r14a",
      "first-page": "530",
      "volume": "A220",
      "year": "1953",
      "journal-title": "Proc. R. Soc. London, Ser. A"
    },
    {
      "key": "2024020817502084200_r15",
      "first-page": "149",
      "volume": "A68",
      "year": "1955",
      "journal-title": "Proc. Phys. Soc. (London)"
    },
    {
      "key": "2024020817502084200_r15a",
      "first-page": "30",
      "volume": "69",
      "year": "1956",
      "journal-title": "Proc. Phys. Soc. London"
    },
    {
      "key": "2024020817502084200_r15b",
      "doi-asserted-by": "crossref",
      "first-page": "767",
      "DOI": "10.1088/0370-1298/69/10/306",
      "volume": "69",
      "year": "1956",
      "journal-title": "Proc. Phys. Soc. London"
    },
    {
      "key": "2024020817502084200_r16"
    },
    {
      "key": "2024020817502084200_r16a"
    },
    {
      "key": "2024020817502084200_r17",
      "doi-asserted-by": "crossref",
      "first-page": "825",
      "DOI": "10.1063/1.1749252",
      "volume": "1",
      "year": "1933",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020817502084200_r18",
      "doi-asserted-by": "crossref",
      "first-page": "150",
      "DOI": "10.1063/1.1700818",
      "volume": "24",
      "year": "1956",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020817502084200_r19",
      "first-page": "237",
      "volume": "4",
      "year": "1954",
      "journal-title": "Acta. Phys. Acad. Sci. Hung."
    },
    {
      "key": "2024020817502084200_r20"
    },
    {
      "key": "2024020817502084200_r21",
      "doi-asserted-by": "crossref",
      "first-page": "782",
      "DOI": "10.1063/1.1749394",
      "volume": "2",
      "year": "1934",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020817502084200_r22",
      "doi-asserted-by": "crossref",
      "first-page": "1254",
      "DOI": "10.1039/tf9534901254",
      "volume": "49",
      "year": "1953",
      "journal-title": "Trans. Faraday Soc."
    },
    {
      "key": "2024020817502084200_r24",
      "doi-asserted-by": "crossref",
      "first-page": "1474",
      "DOI": "10.1103/PhysRev.97.1474",
      "volume": "97",
      "year": "1955",
      "journal-title": "Phys. Rev."
    },
    {
      "key": "2024020817502084200_r25",
      "first-page": "349",
      "volume": "5",
      "year": "1952",
      "journal-title": "Arkiv Fysik"
    },
    {
      "key": "2024020817502084200_r26"
    },
    {
      "key": "2024020817502084200_r27",
      "doi-asserted-by": "crossref",
      "first-page": "70",
      "DOI": "10.1063/1.1743266",
      "volume": "26",
      "year": "1957",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020817502084200_r28",
      "doi-asserted-by": "crossref",
      "first-page": "1092",
      "DOI": "10.1063/1.1743477",
      "volume": "26",
      "year": "1957",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020817502084200_r29"
    },
    {
      "key": "2024020817502084200_r29a"
    },
    {
      "key": "2024020817502084200_r30"
    },
    {
      "key": "2024020817502084200_r30a"
    },
    {
      "key": "2024020817502084200_r31"
    },
    {
      "key": "2024020817502084200_r32"
    },
    {
      "key": "2024020817502084200_r33",
      "doi-asserted-by": "crossref",
      "first-page": "332",
      "DOI": "10.1063/1.1742881",
      "volume": "25",
      "year": "1956",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024020817502084200_r34"
    },
    {
      "key": "2024020817502084200_r35"
    },
    {
      "key": "2024020817502084200_r36",
      "doi-asserted-by": "crossref",
      "first-page": "69",
      "DOI": "10.1103/RevModPhys.23.69",
      "volume": "23",
      "year": "1951",
      "journal-title": "Revs. Modern Phys."
    },
    {
      "key": "2024020817502084200_r37",
      "first-page": "1094",
      "volume": "239",
      "year": "1955",
      "journal-title": "Compt. Rend."
    },
    {
      "key": "2024020817502084200_r38"
    },
    {
      "key": "2024020817502084200_r39",
      "doi-asserted-by": "crossref",
      "first-page": "1561",
      "DOI": "10.1063/1.1747540",
      "volume": "18",
      "year": "1950",
      "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/28/4/532/18813918/532_1_online.pdf",
      "content-type": "application/pdf",
      "content-version": "vor",
      "intended-application": "syndication"
    },
    {
      "URL": "https://pubs.aip.org/aip/jcp/article-pdf/28/4/532/18813918/532_1_online.pdf",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2024,
        2,
        8
      ]
    ],
    "date-time": "2024-02-08T18:38:45Z",
    "timestamp": 1707417525000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://pubs.aip.org/jcp/article/28/4/532/78090/Role-of-Atomic-Valence-States-in-Molecular-Energy"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        1958,
        4,
        1
      ]
    ]
  },
  "references-count": 44,
  "journal-issue": {
    "issue": "4",
    "published-print": {
      "date-parts": [
        [
          1958,
          4,
          1
        ]
      ]
    }
  },
  "URL": "http://dx.doi.org/10.1063/1.1744189",
  "relation": {},
  "ISSN": [
    "0021-9606",
    "1089-7690"
  ],
  "subject": [],
  "published-other": {
    "date-parts": [
      [
        1958,
        4
      ]
    ]
  },
  "published": {
    "date-parts": [
      [
        1958,
        4,
        1
      ]
    ]
  }
}