DOI: 10.1098/rspa.1960.0200. The effect of fluorine on the electronic spectra and ionization potentials of molecules

The effect of fluorine on the electronic spectra and ionization potentials of molecules

10.1098/rspa.1960.0200

Crossref journal-article

The Royal Society

Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences (175)

Abstract

The effect of substituents on the spectra and ionization potentials of electrons in chromophoric groups can in a general way be divided into two major contributions, namely, ( a ) inductive effects which act mainly by changing the binding of electrons in the ground state, and ( b ) resonance effects which stabilize the molecular ion. When the substituent is a fluorine atom these effects are large but of opposite sign. The magnitude of the inductive effect is shown to be in some cases as much as several electron volts by considering sets of molecules where resonance stabilization of the molecular ion is negligible, for example, hydrocarbons and their perfluoroderivatives, NH 3 and NF 3 , the perfluoromethyl halides, etc. In other classes of molecules, such as the trifluoromethyl radicals, the fluorinated ethylenes and aromatics, large resonance stabilization of the molecular ion occurs along with the inductive effect and as these are of opposite sign, relatively small changes of ionization potential result from the substitution. The study of the dependence of increases of ionization potential due to inductive effects on the distance of the substituted fluorine from a chromophore shows how this is reduced as the separation increases. Many of the longer wavelength bands of various chromophores show shifts on substitution which are in the opposite direction to the changes which occur in the ionization potential. It is suggested that these can in many cases be attributed to the different spatial dependence of resonance and inductive effects. The interplay of this spatial variation and the dimensions of the upper orbital, especially when this has a large overlap with the substituting group, can produce energy changes in the excited orbitals which make the bands appear to behave anomolously on substitution. New values for the ionization potentials of the fluorinated ethylenes, aromatics and alkyl halides are given.

Bibliography

The effect of fluorine on the electronic spectra and ionization potentials of molecules. (1960). Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences, 258(1295), 459â469.

Authors 0

None

References 22 Referenced 72

Dibeler V. H . Reese R . M. & Mohler F . L. 1952 Rev. 87 213.
Dibeler V. H . Reese R . M. & Mohler F .
Dibeler V. H . Reese R. M. & Mohler F .
{'key': 'p_4', 'first-page': '113', 'article-title': 'Res. Bur. Stand', 'volume': '57', 'author': 'Dibeler V. H .', 'year': '1956', 'journal-title': 'Wash.'} / Wash. / Res. Bur. Stand by Dibeler V. H . (1956)
{'key': 'p_5', 'first-page': '349', 'article-title': 'J', 'volume': '24', 'author': 'Farm J .', 'year': '1956', 'journal-title': 'Chem. Phys.'} / Chem. Phys. / J by Farm J . (1956)
{'key': 'p_6', 'first-page': '723', 'article-title': 'A n n', 'volume': '9', 'author': 'Goldstein L.', 'year': '1938', 'journal-title': 'Phys. Paris'} / Phys. Paris / A n n by Goldstein L. (1938)
{'key': 'p_7', 'first-page': '52', 'article-title': 'Disc', 'volume': '9', 'author': 'Price W .', 'year': '1950', 'journal-title': 'Faraday Soc.'} / Faraday Soc. / Disc by Price W . (1950)
{'key': 'p_8', 'first-page': '523', 'article-title': 'Canad. J', 'volume': '34', 'author': 'Shoosm J .', 'year': '1956', 'journal-title': 'Phys.'} / Phys. / Canad. J by Shoosm J . (1956)
{'key': 'p_9', 'first-page': '476', 'article-title': 'Proc. P hys', 'volume': '71', 'author': 'Johns J .', 'year': '1958', 'journal-title': 'Soc. A'} / Soc. A / Proc. P hys by Johns J . (1958)
10.6028/jres.049.035
{'key': 'p_11', 'first-page': '1021', 'article-title': 'J', 'volume': '20', 'author': 'Morrison J .', 'year': '1952', 'journal-title': 'Chem. Phys.'} / Chem. Phys. / J by Morrison J . (1952)
{'key': 'p_12', 'first-page': '439', 'article-title': 'J', 'volume': '3', 'author': 'Price W .', 'year': '1935', 'journal-title': 'Chem. Phys.'} / Chem. Phys. / J by Price W . (1935)
Price W . C. 1936 J . Chem.
10.1021/cr60129a005
{'key': 'p_15', 'first-page': '45', 'article-title': 'Spectrochim', 'volume': '14', 'author': 'Price W. C.', 'year': '1959', 'journal-title': 'Acta'} / Acta / Spectrochim by Price W. C. (1959)
Reese R . M. & Dibeler V. H . 1956
10.1039/df9511000035
{'key': 'p_18', 'first-page': '6179', 'article-title': 'J . Am er', 'volume': '81', 'author': 'Stokes S.', 'year': '1959', 'journal-title': 'Chem. Soc.'} / Chem. Soc. / J . Am er by Stokes S. (1959)
{'key': 'p_19', 'first-page': '35', 'article-title': 'Trans', 'volume': '41', 'year': '1945', 'journal-title': 'Faraday Soc.'} / Faraday Soc. / Trans (1945)
{'key': 'p_20', 'first-page': '56', 'article-title': 'Trans', 'volume': '42', 'year': '1946', 'journal-title': 'Faraday Soc.'} / Faraday Soc. / Trans (1946)
W alsh A. D. 1953 J . Chem. Soc. p. 2301. (10.1039/jr9530002301)
W arren J . W . & Craggs J . D. Petroleum . 1952 M ass Spectrometry p. 36. London: In stitu te of

Dates

Type	When
Created	18 years, 8 months ago (Dec. 15, 2006, 2:56 p.m.)
Deposited	4 years, 6 months ago (Feb. 17, 2021, 6:31 p.m.)
Indexed	2 months ago (July 2, 2025, 11:40 a.m.)
Issued	64 years, 9 months ago (Nov. 8, 1960)
Published	64 years, 9 months ago (Nov. 8, 1960)
Published Online	28 years, 8 months ago (Jan. 1, 1997)
Published Print	64 years, 9 months ago (Nov. 8, 1960)

Funders 0

None

BibTeX

@article{1960, volume={258}, ISSN={2053-9169}, url={http://dx.doi.org/10.1098/rspa.1960.0200}, DOI={10.1098/rspa.1960.0200}, number={1295}, journal={Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences}, publisher={The Royal Society}, year={1960}, month=nov, pages={459–469} }

JSON

{
  "indexed": {
    "date-parts": [
      [
        2025,
        7,
        2
      ]
    ],
    "date-time": "2025-07-02T15:40:42Z",
    "timestamp": 1751470842265
  },
  "reference-count": 22,
  "publisher": "The Royal Society",
  "issue": "1295",
  "license": [
    {
      "start": {
        "date-parts": [
          [
            1960,
            11,
            8
          ]
        ],
        "date-time": "1960-11-08T00:00:00Z",
        "timestamp": -288662400000
      },
      "content-version": "tdm",
      "delay-in-days": 0,
      "URL": "https://royalsociety.org/journals/ethics-policies/data-sharing-mining/"
    }
  ],
  "content-domain": {
    "domain": [],
    "crossmark-restriction": false
  },
  "published-print": {
    "date-parts": [
      [
        1960,
        11,
        8
      ]
    ]
  },
  "abstract": "<jats:p>\n            The effect of substituents on the spectra and ionization potentials of electrons in chromophoric groups can in a general way be divided into two major contributions, namely, (\n            <jats:italic>a</jats:italic>\n            ) inductive effects which act mainly by changing the binding of electrons in the ground state, and (\n            <jats:italic>b</jats:italic>\n            ) resonance effects which stabilize the molecular ion. When the substituent is a fluorine atom these effects are large but of opposite sign. The magnitude of the inductive effect is shown to be in some cases as much as several electron volts by considering sets of molecules where resonance stabilization of the molecular ion is negligible, for example, hydrocarbons and their perfluoroderivatives, NH\n            <jats:sub>3</jats:sub>\n            and NF\n            <jats:sub>3</jats:sub>\n            , the perfluoromethyl halides, etc. In other classes of molecules, such as the trifluoromethyl radicals, the fluorinated ethylenes and aromatics, large resonance stabilization of the molecular ion occurs along with the inductive effect and as these are of opposite sign, relatively small changes of ionization potential result from the substitution. The study of the dependence of increases of ionization potential due to inductive effects on the distance of the substituted fluorine from a chromophore shows how this is reduced as the separation increases. Many of the longer wavelength bands of various chromophores show shifts on substitution which are in the opposite direction to the changes which occur in the ionization potential. It is suggested that these can in many cases be attributed to the different spatial dependence of resonance and inductive effects. The interplay of this spatial variation and the dimensions of the upper orbital, especially when this has a large overlap with the substituting group, can produce energy changes in the excited orbitals which make the bands appear to behave anomolously on substitution. New values for the ionization potentials of the fluorinated ethylenes, aromatics and alkyl halides are given.\n          </jats:p>",
  "DOI": "10.1098/rspa.1960.0200",
  "type": "journal-article",
  "created": {
    "date-parts": [
      [
        2006,
        12,
        15
      ]
    ],
    "date-time": "2006-12-15T19:56:36Z",
    "timestamp": 1166212596000
  },
  "page": "459-469",
  "source": "Crossref",
  "is-referenced-by-count": 72,
  "title": "The effect of fluorine on the electronic spectra and ionization potentials of molecules",
  "prefix": "10.1098",
  "volume": "258",
  "member": "175",
  "published-online": {
    "date-parts": [
      [
        1997,
        1
      ]
    ]
  },
  "reference": [
    {
      "key": "p_1",
      "unstructured": "Dibeler V. H . Reese R . M. & Mohler F . L. 1952 Rev. 87 213."
    },
    {
      "key": "p_2",
      "unstructured": "Dibeler V. H . Reese R . M. & Mohler F ."
    },
    {
      "key": "p_3",
      "unstructured": "Dibeler V. H . Reese R. M. & Mohler F ."
    },
    {
      "key": "p_4",
      "first-page": "113",
      "article-title": "Res. Bur. Stand",
      "volume": "57",
      "author": "Dibeler V. H .",
      "year": "1956",
      "journal-title": "Wash."
    },
    {
      "key": "p_5",
      "first-page": "349",
      "article-title": "J",
      "volume": "24",
      "author": "Farm J .",
      "year": "1956",
      "journal-title": "Chem. Phys."
    },
    {
      "key": "p_6",
      "first-page": "723",
      "article-title": "A n n",
      "volume": "9",
      "author": "Goldstein L.",
      "year": "1938",
      "journal-title": "Phys. Paris"
    },
    {
      "key": "p_7",
      "first-page": "52",
      "article-title": "Disc",
      "volume": "9",
      "author": "Price W .",
      "year": "1950",
      "journal-title": "Faraday Soc."
    },
    {
      "key": "p_8",
      "first-page": "523",
      "article-title": "Canad. J",
      "volume": "34",
      "author": "Shoosm J .",
      "year": "1956",
      "journal-title": "Phys."
    },
    {
      "key": "p_9",
      "first-page": "476",
      "article-title": "Proc. P hys",
      "volume": "71",
      "author": "Johns J .",
      "year": "1958",
      "journal-title": "Soc. A"
    },
    {
      "key": "p_10",
      "doi-asserted-by": "publisher",
      "DOI": "10.6028/jres.049.035"
    },
    {
      "key": "p_11",
      "first-page": "1021",
      "article-title": "J",
      "volume": "20",
      "author": "Morrison J .",
      "year": "1952",
      "journal-title": "Chem. Phys."
    },
    {
      "key": "p_12",
      "first-page": "439",
      "article-title": "J",
      "volume": "3",
      "author": "Price W .",
      "year": "1935",
      "journal-title": "Chem. Phys."
    },
    {
      "key": "p_13",
      "unstructured": "Price W . C. 1936 J . Chem."
    },
    {
      "key": "p_14",
      "doi-asserted-by": "publisher",
      "DOI": "10.1021/cr60129a005"
    },
    {
      "key": "p_15",
      "first-page": "45",
      "article-title": "Spectrochim",
      "volume": "14",
      "author": "Price W. C.",
      "year": "1959",
      "journal-title": "Acta"
    },
    {
      "key": "p_16",
      "unstructured": "Reese R . M. & Dibeler V. H . 1956"
    },
    {
      "key": "p_17",
      "doi-asserted-by": "publisher",
      "DOI": "10.1039/df9511000035"
    },
    {
      "key": "p_18",
      "first-page": "6179",
      "article-title": "J . Am er",
      "volume": "81",
      "author": "Stokes S.",
      "year": "1959",
      "journal-title": "Chem. Soc."
    },
    {
      "key": "p_19",
      "first-page": "35",
      "article-title": "Trans",
      "volume": "41",
      "year": "1945",
      "journal-title": "Faraday Soc."
    },
    {
      "key": "p_20",
      "first-page": "56",
      "article-title": "Trans",
      "volume": "42",
      "year": "1946",
      "journal-title": "Faraday Soc."
    },
    {
      "key": "p_21",
      "doi-asserted-by": "crossref",
      "unstructured": "W alsh A. D. 1953 J . Chem. Soc. p. 2301.",
      "DOI": "10.1039/jr9530002301"
    },
    {
      "key": "p_22",
      "unstructured": "W arren J . W . & Craggs J . D. Petroleum . 1952 M ass Spectrometry p. 36. London: In stitu te of"
    }
  ],
  "container-title": "Proceedings of the Royal Society of London. Series A. Mathematical and Physical Sciences",
  "original-title": [],
  "language": "en",
  "link": [
    {
      "URL": "https://royalsocietypublishing.org/doi/pdf/10.1098/rspa.1960.0200",
      "content-type": "application/pdf",
      "content-version": "vor",
      "intended-application": "text-mining"
    },
    {
      "URL": "https://royalsocietypublishing.org/doi/pdf/10.1098/rspa.1960.0200",
      "content-type": "unspecified",
      "content-version": "vor",
      "intended-application": "similarity-checking"
    }
  ],
  "deposited": {
    "date-parts": [
      [
        2021,
        2,
        17
      ]
    ],
    "date-time": "2021-02-17T23:31:46Z",
    "timestamp": 1613604706000
  },
  "score": 1,
  "resource": {
    "primary": {
      "URL": "https://royalsocietypublishing.org/doi/10.1098/rspa.1960.0200"
    }
  },
  "subtitle": [],
  "short-title": [],
  "issued": {
    "date-parts": [
      [
        1960,
        11,
        8
      ]
    ]
  },
  "references-count": 22,
  "journal-issue": {
    "issue": "1295",
    "published-print": {
      "date-parts": [
        [
          1960,
          11,
          8
        ]
      ]
    }
  },
  "alternative-id": [
    "10.1098/rspa.1960.0200"
  ],
  "URL": "http://dx.doi.org/10.1098/rspa.1960.0200",
  "relation": {},
  "ISSN": [
    "0080-4630",
    "2053-9169"
  ],
  "subject": [],
  "container-title-short": "Proc. R. Soc. Lond. A",
  "published": {
    "date-parts": [
      [
        1960,
        11,
        8
      ]
    ]
  }
}