DOI: 10.1063/1.455864. Nonequilibrium solvation effects on reaction rates for model SN2 reactions in water

Nonequilibrium solvation effects on reaction rates for model SN2 reactions in water

10.1063/1.455864

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

Molecular dynamics (MD) simulations of the model SN2 reaction Cl−+CH3Cl→ClCH3+Cl− in water, and variants thereof, are presented. The resulting transmission coefficients κ, that measure the deviations of the rates from the transition state theory (TST) rate predictions due to solvent-induced recrossings, are used to assess the validity of the generalized Langevin equation (GLE)-based Grote–Hynes (GH) theory. The GH predictions are found to agree with the MD results to within the error bars of the calculations for each of the 12 cases examined. This agreement extends from the nonadiabatic regime, where solvent molecule motions are unimportant and κ is determined by static solvent configurations at the transition state, into the polarization caging regime, where solvent motion is critical in determining κ. In contrast, the Kramers theory predictions for κ fall well below the simulation results. The friction kernel in the GLE used to evaluate the GH κ values is determined, from MD simulation, by a fixed-particle time correlation function of the force at the transition state. When this is expressed as a (Fourier) friction spectrum in frequency, marked similarities to the pure solvent spectrum are observed, and are used to identify the water solvent motions that determine the transmission coefficient κ. The deviations of κ from unity, the TST value, are dominated by solvent motions (translational and reorientational) which on the time scale of the recrossings are essentially static configurations. The deviations from the frozen solvent, nonadiabatic limit values κNA are dominated by the hinderd rotations (librations). Finally, the underlying assumptions of the GLE and the GH theory are discussed within the context of the simulation results.

Bibliography

Gertner, B. J., Wilson, K. R., & Hynes, J. T. (1989). Nonequilibrium solvation effects on reaction rates for model SN2 reactions in water. The Journal of Chemical Physics, 90(7), 3537â3558.

Authors 3

Bradley J. Gertner (first)
Kent R. Wilson (additional)
James T. Hynes (additional)

References 151 Referenced 296

10.1063/1.452224 / J. Chem. Phys. (1987)
10.1063/1.452225 / J. Chem. Phys. (1987)
{'key': '2024021007313311600_r3'}
10.1021/ja00322a059 / J. Am Chem. Soc. (1984)
10.1021/ja00287a028 / J. Am. Chem. Soc. (1985)
10.1021/ja00334a080 / J. Am. Chem. Soc. (1984)
{'key': '2024021007313311600_r7'}
10.1021/j100238a003 / J. Phys. Chem. (1983)
{'key': '2024021007313311600_r9', 'first-page': '573', 'volume': '36', 'year': '1984', 'journal-title': 'Annu. Rev. Phys. Chem.'} / Annu. Rev. Phys. Chem. (1984)
10.1039/tf9383400029 / Trans. Faraday Soc. (1938)
10.1021/ja00768a010 / J. Am. Chem. Soc. (1972)
10.1063/1.443392 / J. Chem. Phys. (1982)
10.1063/1.445094 / J. Chem. Phys. (1983)
10.1016/0301-0104(84)85078-8 / Chem. Phys. (1984)
{'key': '2024021007313311600_r15'}
{'key': '2024021007313311600_r16'}
{'key': '2024021007313311600_r17'}
{'key': '2024021007313311600_r18'}
10.1021/ja00761a009 / J. Am. Chem. Soc. (1972)
10.1080/00268977700103001 / Mol. Phys. (1977)
10.1039/f29787401532 / J. Chem. Soc. Faraday Trans. 2 (1978)
{'key': '2024021007313311600_r22', 'first-page': '230', 'volume': '322', 'year': '1982', 'journal-title': 'Proc. Soc. Photo-Optic. Instrum. Engin.'} / Proc. Soc. Photo-Optic. Instrum. Engin. (1982)
{'key': '2024021007313311600_r23'}
10.1155/LC.3.231 / Laser Chem. (1983)
10.1063/1.445829 / J. Chem. Phys. (1983)
10.1021/j150670a041 / J. Phys. Chem. (1984)
10.1063/1.450756 / J. Chem. Phys. (1986)
{'key': '2024021007313311600_r28'}
10.1063/1.438028 / J. Chem. Phys. (1979)
10.1016/0009-2614(80)80487-8 / Chem. Phys. Lett. (1980)
10.1021/j100320a003 / J. Phys. Chem. (1988)
{'key': '2024021007313311600_r31a'}
10.1063/1.455678 / J. Chem. Phys. (1988)
10.1021/j100209a016 / J. Phys. Chem. (1982)
10.1073/pnas.81.2.444 / Proc. Natl. Acad. Sci. U.S.A. (1984)
10.1021/ja00237a013 / J. Am. Chem. Soc. (1987)
10.1016/S0006-3495(84)84016-3 / Biophys. J. (1984)
10.1021/ja00268a007 / J. Am. Chem. Soc. (1986)
{'key': '2024021007313311600_r38'}
10.1021/j100238a015 / J. Phys. Chem. (1983)
{'key': '2024021007313311600_r40', 'first-page': '222', 'volume': '482', 'year': '1987', 'journal-title': 'Ann. N. Y. Acad. Sci.'} / Ann. N. Y. Acad. Sci. (1987)
{'key': '2024021007313311600_r41'}
10.1146/annurev.pc.31.100180.000333 / Annu. Rev. Phys. Chem. (1980)
10.3109/10409238109105437 / CRC Crit. Rev. Biochem. (1981)
10.1021/ar00090a001 / Acc. Chem. Res. (1983)
10.1080/00268978000100171 / Mol. Phys. (1980)
10.1016/0009-2614(86)80029-X / Chem. Phys. Lett. (1986)
10.1063/1.451576 / J. Chem. Phys. (1986)
10.1016/S0031-8914(40)90098-2 / Physica (1940)
10.1063/1.440485 / J. Chem. Phys. (1980)
{'key': '2024021007313311600_r50'}
{'key': '2024021007313311600_r51'}
{'key': '2024021007313311600_r52'}
10.1143/PTP.33.423 / Prog. Theor. Phys. (1965)
10.1088/0034-4885/29/1/306 / Rep. Prog. Phys. (1966)
10.1146/annurev.pc.16.100165.000435 / Annu. Rev. Phys. Chem. (1965)
10.1146/annurev.pc.28.100177.001505 / Annu. Rev. Phys. Chem. (1977)
10.1016/B978-0-12-025507-8.50008-5 / Adv. Magn. Reson. (1974)
10.1002/9780470142592.ch1 / Adv. Chem. Phys. (1979)
{'key': '2024021007313311600_r59'}
{'key': '2024021007313311600_r60', 'first-page': '143', 'volume': '44', 'year': '1980', 'journal-title': 'Adv. Chem. Phys.'} / Adv. Chem. Phys. (1980)
10.1063/1.432526 / J. Chem. Phys. (1976)
10.1146/annurev.pc.31.100180.001535 / Annu. Rev. Phys. Chem. (1980)
10.1051/rphysap:0198700220120178700 / Rev. Phys. Appl. (1987)
10.1063/1.451294 / J. Chem. Phys. (1986)
10.1007/BF01008729 / J. Stat. Phys. (1973)
10.1063/1.440551 / J. Chem. Phys. (1980)
10.1063/1.443093 / J. Chem. Phys. (1982)
{'key': '2024021007313311600_r68', 'first-page': '61', 'volume': '53', 'year': '1983', 'journal-title': 'Adv. Chem. Phys.'} / Adv. Chem. Phys. (1983)
10.1103/PhysRevA.26.1168 / Phys. Rev. A (1982)
{'key': '2024021007313311600_r69a', 'first-page': '389', 'volume': '62', 'year': '1985', 'journal-title': 'Adv. Chem. Phys.'} / Adv. Chem. Phys. (1985)
10.1016/0375-9601(84)90343-8 / Phys. Lett. A (1984)
10.1063/1.449893 / J. Chem. Phys. (1986)
10.1063/1.454812 / J. Chem. Phys. (1988)
{'key': '2024021007313311600_r70'}
{'key': '2024021007313311600_r71'}
{'key': '2024021007313311600_r72'}
{'key': '2024021007313311600_r73'}
10.1063/1.442716 / J. Chem. Phys. (1982)
10.1016/0021-9991(76)90059-0 / J. Comput. Phys. (1976)
{'key': '2024021007313311600_r76'}
{'key': '2024021007313311600_r77'}
10.1016/0301-0104(77)85160-4 / Chem. Phys. (1977)
10.1246/bcsj.38.814 / Bull. Chem. Soc. Jpn. (1965)
{'key': '2024021007313311600_r80'}
10.1039/df9623300173 / Discuss. Faraday Soc. (1962)
10.1063/1.1679032 / J. Chem. Phys. (1973)
{'key': '2024021007313311600_r83'}
10.1063/1.440733 / J. Chem. Phys. (1980)
{'key': '2024021007313311600_r85'}
{'key': '2024021007313311600_r86'}
{'key': '2024021007313311600_r87'}
{'key': '2024021007313311600_r88'}
10.1063/1.449476 / J. Chem. Phys. (1985)
10.1021/j100270a014 / J. Phys. Chem. (1985)
10.1021/j100324a007 / J. Phys. Chem. (1988)
10.1063/1.440484 / J. Chem. Phys. (1980)
10.1063/1.1731099 / J. Chem. Phys. (1960)
10.1063/1.436049 / J. Chem. Phys. (1978)
10.1007/BF01010840 / J. Stat. Phys. (1986)
{'key': '2024021007313311600_r96'}
10.1021/j100322a038 / J. Phys. Chem. (1988)
10.1063/1.1677461 / J. Chem. Phys. (1972)
10.1063/1.435917 / J. Chem. Phys. (1978)
{'key': '2024021007313311600_r100'}
{'key': '2024021007313311600_r101'}
{'key': '2024021007313311600_r102'}
{'key': '2024021007313311600_r103'}
{'key': '2024021007313311600_r104'}
10.1063/1.450956 / J. Chem. Phys. (1986)
10.1063/1.453487 / J. Chem. Phys. (1987)
{'key': '2024021007313311600_r105'}
10.1016/0009-2614(85)80084-1 / Chem. Phys. Lett. (1985)
{'key': '2024021007313311600_r106'}
10.1063/1.441634 / J. Chem. Phys. (1981)
10.1063/1.442331 / J. Chem. Phys. (1981)
10.1063/1.443951 / J. Chem. Phys. (1982)
10.1063/1.450425 / J. Chem. Phys. (1986)
{'key': '2024021007313311600_r110'}
10.1063/1.446044 / J. Chem. Phys. (1983)
{'key': '2024021007313311600_r112'}
{'key': '2024021007313311600_r113'}
{'key': '2024021007313311600_r114'}
{'key': '2024021007313311600_r115'}
10.1016/0378-4371(75)90162-4 / Physica A (1975)
{'key': '2024021007313311600_r116a', 'first-page': '425', 'volume': '81', 'year': '1975', 'journal-title': 'Physica A'} / Physica A (1975)
10.1063/1.1675379 / J. Chem. Phys. (1971)
{'key': '2024021007313311600_r118'}
10.1063/1.452574 / J. Chem. Phys. (1987)
10.1103/PhysRevA.3.2049 / Phys. Rev. A (1971)
10.1007/BF01010844 / J. Stat. Phys. (1986)
{'key': '2024021007313311600_r122'}
10.1063/1.442038 / J. Chem. Phys. (1981)
10.1021/j100303a019 / J. Phys. Chem. (1987)
10.1021/j100266a008 / J. Phys. Chem. (1985)
10.1063/1.454030 / J. Chem. Phys. (1988)
10.1063/1.454383 / J. Chem. Phys. (1988)
10.1063/1.454747 / J. Chem. Phys. (1988)
{'key': '2024021007313311600_r128'}
{'key': '2024021007313311600_r129'}
10.1021/j100323a016 / J. Phys. Chem. (1988)
10.1063/1.455649 / J. Chem. Phys. (1988)
10.1016/0022-0728(86)80519-8 / J. Electroanal. Chem. (1986)
10.1021/j150664a047 / J. Phys. Chem. (1984)
{'key': '2024021007313311600_r134', 'first-page': '357', 'volume': '70', 'year': '1988', 'journal-title': 'Adv. Chem. Phys.'} / Adv. Chem. Phys. (1988)
{'key': '2024021007313311600_r135', 'first-page': '489', 'volume': '70', 'year': '1988', 'journal-title': 'Adv. Chem. Phys.'} / Adv. Chem. Phys. (1988)
{'key': '2024021007313311600_r136'}
{'key': '2024021007313311600_r137'}
{'key': '2024021007313311600_r138'}
{'key': '2024021007313311600_r139'}
{'key': '2024021007313311600_r140'}

Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 9:10 a.m.)
Deposited	1 year, 6 months ago (Feb. 10, 2024, 4:27 a.m.)
Indexed	3 months ago (May 27, 2025, 5:05 a.m.)
Issued	36 years, 4 months ago (April 1, 1989)
Published	36 years, 4 months ago (April 1, 1989)
Published Print	36 years, 4 months ago (April 1, 1989)

Funders 0

None

BibTeX

@article{Gertner_1989, title={Nonequilibrium solvation effects on reaction rates for model SN2 reactions in water}, volume={90}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.455864}, DOI={10.1063/1.455864}, number={7}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Gertner, Bradley J. and Wilson, Kent R. and Hynes, James T.}, year={1989}, month=apr, pages={3537–3558} }

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  "abstract": "<jats:p>Molecular dynamics (MD) simulations of the model SN2 reaction Cl\u2212+CH3Cl\u2192ClCH3+Cl\u2212 in water, and variants thereof, are presented. The resulting transmission coefficients \u03ba, that measure the deviations of the rates from the transition state theory (TST) rate predictions due to solvent-induced recrossings, are used to assess the validity of the generalized Langevin equation (GLE)-based Grote\u2013Hynes (GH) theory. The GH predictions are found to agree with the MD results to within the error bars of the calculations for each of the 12 cases examined. This agreement extends from the nonadiabatic regime, where solvent molecule motions are unimportant and \u03ba is determined by static solvent configurations at the transition state, into the polarization caging regime, where solvent motion is critical in determining \u03ba. In contrast, the Kramers theory predictions for \u03ba fall well below the simulation results. The friction kernel in the GLE used to evaluate the GH \u03ba values is determined, from MD simulation, by a fixed-particle time correlation function of the force at the transition state. When this is expressed as a (Fourier) friction spectrum in frequency, marked similarities to the pure solvent spectrum are observed, and are used to identify the water solvent motions that determine the transmission coefficient \u03ba. The deviations of \u03ba from unity, the TST value, are dominated by solvent motions (translational and reorientational) which on the time scale of the recrossings are essentially static configurations. The deviations from the frozen solvent, nonadiabatic limit values \u03baNA are dominated by the hinderd rotations (librations). Finally, the underlying assumptions of the GLE and the GH theory are discussed within the context of the simulation results.</jats:p>",
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      "DOI": "10.1063/1.452225",
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    {
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      "doi-asserted-by": "crossref",
      "first-page": "3049",
      "DOI": "10.1021/ja00322a059",
      "volume": "106",
      "year": "1984",
      "journal-title": "J. Am Chem. Soc."
    },
    {
      "key": "2024021007313311600_r5",
      "doi-asserted-by": "crossref",
      "first-page": "154",
      "DOI": "10.1021/ja00287a028",
      "volume": "107",
      "year": "1985",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "2024021007313311600_r6",
      "doi-asserted-by": "crossref",
      "first-page": "6867",
      "DOI": "10.1021/ja00334a080",
      "volume": "106",
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      "journal-title": "J. Am. Chem. Soc."
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    {
      "key": "2024021007313311600_r7"
    },
    {
      "key": "2024021007313311600_r8",
      "doi-asserted-by": "crossref",
      "first-page": "2664",
      "DOI": "10.1021/j100238a003",
      "volume": "87",
      "year": "1983",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024021007313311600_r9",
      "first-page": "573",
      "volume": "36",
      "year": "1984",
      "journal-title": "Annu. Rev. Phys. Chem."
    },
    {
      "key": "2024021007313311600_r10",
      "doi-asserted-by": "crossref",
      "first-page": "29",
      "DOI": "10.1039/tf9383400029",
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      "year": "1938",
      "journal-title": "Trans. Faraday Soc."
    },
    {
      "key": "2024021007313311600_r11",
      "doi-asserted-by": "crossref",
      "first-page": "4451",
      "DOI": "10.1021/ja00768a010",
      "volume": "94",
      "year": "1972",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "2024021007313311600_r12",
      "doi-asserted-by": "crossref",
      "first-page": "2993",
      "DOI": "10.1063/1.443392",
      "volume": "76",
      "year": "1982",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r13",
      "doi-asserted-by": "crossref",
      "first-page": "4174",
      "DOI": "10.1063/1.445094",
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      "year": "1983",
      "journal-title": "J. Chem. Phys."
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    {
      "key": "2024021007313311600_r14",
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      "first-page": "21",
      "DOI": "10.1016/0301-0104(84)85078-8",
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      "first-page": "1532",
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      "year": "1982",
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      "key": "2024021007313311600_r24",
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      "DOI": "10.1155/LC.3.231",
      "volume": "3",
      "year": "1983",
      "journal-title": "Laser Chem."
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    {
      "key": "2024021007313311600_r25",
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      "first-page": "784",
      "DOI": "10.1063/1.445829",
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      "first-page": "6720",
      "DOI": "10.1021/j150670a041",
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      "journal-title": "J. Phys. Chem."
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      "first-page": "6151",
      "DOI": "10.1063/1.450756",
      "volume": "84",
      "year": "1986",
      "journal-title": "J. Chem. Phys."
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    {
      "key": "2024021007313311600_r28"
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    {
      "key": "2024021007313311600_r29",
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      "DOI": "10.1063/1.438028",
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      "year": "1979",
      "journal-title": "J. Chem. Phys."
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      "DOI": "10.1016/0009-2614(80)80487-8",
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      "journal-title": "Chem. Phys. Lett."
    },
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      "first-page": "2401",
      "DOI": "10.1021/j100320a003",
      "volume": "92",
      "year": "1988",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024021007313311600_r31a"
    },
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      "key": "2024021007313311600_r32",
      "doi-asserted-by": "crossref",
      "first-page": "4833",
      "DOI": "10.1063/1.455678",
      "volume": "89",
      "year": "1988",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r33",
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      "first-page": "2218",
      "DOI": "10.1021/j100209a016",
      "volume": "86",
      "year": "1982",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024021007313311600_r34",
      "doi-asserted-by": "crossref",
      "first-page": "444",
      "DOI": "10.1073/pnas.81.2.444",
      "volume": "81",
      "year": "1984",
      "journal-title": "Proc. Natl. Acad. Sci. U.S.A."
    },
    {
      "key": "2024021007313311600_r35",
      "doi-asserted-by": "crossref",
      "first-page": "715",
      "DOI": "10.1021/ja00237a013",
      "volume": "109",
      "year": "1987",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "2024021007313311600_r36",
      "doi-asserted-by": "crossref",
      "first-page": "229",
      "DOI": "10.1016/S0006-3495(84)84016-3",
      "volume": "46",
      "year": "1984",
      "journal-title": "Biophys. J."
    },
    {
      "key": "2024021007313311600_r37",
      "doi-asserted-by": "crossref",
      "first-page": "1755",
      "DOI": "10.1021/ja00268a007",
      "volume": "108",
      "year": "1986",
      "journal-title": "J. Am. Chem. Soc."
    },
    {
      "key": "2024021007313311600_r38"
    },
    {
      "key": "2024021007313311600_r39",
      "doi-asserted-by": "crossref",
      "first-page": "2764",
      "DOI": "10.1021/j100238a015",
      "volume": "87",
      "year": "1983",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024021007313311600_r40",
      "first-page": "222",
      "volume": "482",
      "year": "1987",
      "journal-title": "Ann. N. Y. Acad. Sci."
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    {
      "key": "2024021007313311600_r41"
    },
    {
      "key": "2024021007313311600_r42",
      "doi-asserted-by": "crossref",
      "first-page": "29",
      "DOI": "10.1146/annurev.pc.31.100180.000333",
      "volume": "31",
      "year": "1980",
      "journal-title": "Annu. Rev. Phys. Chem."
    },
    {
      "key": "2024021007313311600_r43",
      "doi-asserted-by": "crossref",
      "first-page": "293",
      "DOI": "10.3109/10409238109105437",
      "volume": "9",
      "year": "1981",
      "journal-title": "CRC Crit. Rev. Biochem."
    },
    {
      "key": "2024021007313311600_r44",
      "doi-asserted-by": "crossref",
      "first-page": "187",
      "DOI": "10.1021/ar00090a001",
      "volume": "16",
      "year": "1983",
      "journal-title": "Acc. Chem. Res."
    },
    {
      "key": "2024021007313311600_r45",
      "doi-asserted-by": "crossref",
      "first-page": "207",
      "DOI": "10.1080/00268978000100171",
      "volume": "39",
      "year": "1980",
      "journal-title": "Mol. Phys."
    },
    {
      "key": "2024021007313311600_r46",
      "doi-asserted-by": "crossref",
      "first-page": "394",
      "DOI": "10.1016/0009-2614(86)80029-X",
      "volume": "123",
      "year": "1986",
      "journal-title": "Chem. Phys. Lett."
    },
    {
      "key": "2024021007313311600_r47",
      "doi-asserted-by": "crossref",
      "first-page": "5625",
      "DOI": "10.1063/1.451576",
      "volume": "85",
      "year": "1986",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r48",
      "doi-asserted-by": "crossref",
      "first-page": "284",
      "DOI": "10.1016/S0031-8914(40)90098-2",
      "volume": "7",
      "year": "1940",
      "journal-title": "Physica"
    },
    {
      "key": "2024021007313311600_r49",
      "doi-asserted-by": "crossref",
      "first-page": "2715",
      "DOI": "10.1063/1.440485",
      "volume": "73",
      "year": "1980",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r50"
    },
    {
      "key": "2024021007313311600_r51"
    },
    {
      "key": "2024021007313311600_r52"
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    {
      "key": "2024021007313311600_r53",
      "doi-asserted-by": "crossref",
      "first-page": "423",
      "DOI": "10.1143/PTP.33.423",
      "volume": "33",
      "year": "1965",
      "journal-title": "Prog. Theor. Phys."
    },
    {
      "key": "2024021007313311600_r54",
      "doi-asserted-by": "crossref",
      "first-page": "255",
      "DOI": "10.1088/0034-4885/29/1/306",
      "volume": "29",
      "year": "1966",
      "journal-title": "Rep. Prog. Phys."
    },
    {
      "key": "2024021007313311600_r55",
      "doi-asserted-by": "crossref",
      "first-page": "67",
      "DOI": "10.1146/annurev.pc.16.100165.000435",
      "volume": "16",
      "year": "1965",
      "journal-title": "Annu. Rev. Phys. Chem."
    },
    {
      "key": "2024021007313311600_r56",
      "doi-asserted-by": "crossref",
      "first-page": "301",
      "DOI": "10.1146/annurev.pc.28.100177.001505",
      "volume": "28",
      "year": "1977",
      "journal-title": "Annu. Rev. Phys. Chem."
    },
    {
      "key": "2024021007313311600_r57",
      "doi-asserted-by": "crossref",
      "first-page": "71",
      "DOI": "10.1016/B978-0-12-025507-8.50008-5",
      "volume": "7",
      "year": "1974",
      "journal-title": "Adv. Magn. Reson."
    },
    {
      "key": "2024021007313311600_r58",
      "doi-asserted-by": "crossref",
      "first-page": "1",
      "DOI": "10.1002/9780470142592.ch1",
      "volume": "40",
      "year": "1979",
      "journal-title": "Adv. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r59"
    },
    {
      "key": "2024021007313311600_r60",
      "first-page": "143",
      "volume": "44",
      "year": "1980",
      "journal-title": "Adv. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r61",
      "doi-asserted-by": "crossref",
      "first-page": "2375",
      "DOI": "10.1063/1.432526",
      "volume": "64",
      "year": "1976",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r62",
      "doi-asserted-by": "crossref",
      "first-page": "319",
      "DOI": "10.1146/annurev.pc.31.100180.001535",
      "volume": "31",
      "year": "1980",
      "journal-title": "Annu. Rev. Phys. Chem."
    },
    {
      "key": "2024021007313311600_r63",
      "doi-asserted-by": "crossref",
      "first-page": "1787",
      "DOI": "10.1051/rphysap:0198700220120178700",
      "volume": "22",
      "year": "1987",
      "journal-title": "Rev. Phys. Appl."
    },
    {
      "key": "2024021007313311600_r64",
      "doi-asserted-by": "crossref",
      "first-page": "865",
      "DOI": "10.1063/1.451294",
      "volume": "85",
      "year": "1986",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r65",
      "doi-asserted-by": "crossref",
      "first-page": "215",
      "DOI": "10.1007/BF01008729",
      "volume": "9",
      "year": "1973",
      "journal-title": "J. Stat. Phys."
    },
    {
      "key": "2024021007313311600_r66",
      "doi-asserted-by": "crossref",
      "first-page": "3145",
      "DOI": "10.1063/1.440551",
      "volume": "73",
      "year": "1980",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r67",
      "doi-asserted-by": "crossref",
      "first-page": "1007",
      "DOI": "10.1063/1.443093",
      "volume": "76",
      "year": "1982",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r68",
      "first-page": "61",
      "volume": "53",
      "year": "1983",
      "journal-title": "Adv. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r69",
      "doi-asserted-by": "crossref",
      "first-page": "1168",
      "DOI": "10.1103/PhysRevA.26.1168",
      "volume": "26",
      "year": "1982",
      "journal-title": "Phys. Rev. A"
    },
    {
      "key": "2024021007313311600_r69a",
      "first-page": "389",
      "volume": "62",
      "year": "1985",
      "journal-title": "Adv. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r69b",
      "doi-asserted-by": "crossref",
      "first-page": "15",
      "DOI": "10.1016/0375-9601(84)90343-8",
      "volume": "100",
      "year": "1984",
      "journal-title": "Phys. Lett. A"
    },
    {
      "key": "2024021007313311600_r69c",
      "doi-asserted-by": "crossref",
      "first-page": "5830",
      "DOI": "10.1063/1.449893",
      "volume": "84",
      "year": "1986",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r69d",
      "doi-asserted-by": "crossref",
      "first-page": "4300",
      "DOI": "10.1063/1.454812",
      "volume": "89",
      "year": "1988",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r70"
    },
    {
      "key": "2024021007313311600_r71"
    },
    {
      "key": "2024021007313311600_r72"
    },
    {
      "key": "2024021007313311600_r73"
    },
    {
      "key": "2024021007313311600_r74",
      "doi-asserted-by": "crossref",
      "first-page": "637",
      "DOI": "10.1063/1.442716",
      "volume": "76",
      "year": "1982",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r75",
      "doi-asserted-by": "crossref",
      "first-page": "130",
      "DOI": "10.1016/0021-9991(76)90059-0",
      "volume": "20",
      "year": "1976",
      "journal-title": "J. Comput. Phys."
    },
    {
      "key": "2024021007313311600_r76"
    },
    {
      "key": "2024021007313311600_r77"
    },
    {
      "key": "2024021007313311600_r78",
      "doi-asserted-by": "crossref",
      "first-page": "367",
      "DOI": "10.1016/0301-0104(77)85160-4",
      "volume": "26",
      "year": "1977",
      "journal-title": "Chem. Phys."
    },
    {
      "key": "2024021007313311600_r79",
      "doi-asserted-by": "crossref",
      "first-page": "814",
      "DOI": "10.1246/bcsj.38.814",
      "volume": "38",
      "year": "1965",
      "journal-title": "Bull. Chem. Soc. Jpn."
    },
    {
      "key": "2024021007313311600_r80"
    },
    {
      "key": "2024021007313311600_r81",
      "doi-asserted-by": "crossref",
      "first-page": "173",
      "DOI": "10.1039/df9623300173",
      "volume": "33",
      "year": "1962",
      "journal-title": "Discuss. Faraday Soc."
    },
    {
      "key": "2024021007313311600_r82",
      "doi-asserted-by": "crossref",
      "first-page": "4684",
      "DOI": "10.1063/1.1679032",
      "volume": "58",
      "year": "1973",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r83"
    },
    {
      "key": "2024021007313311600_r84",
      "doi-asserted-by": "crossref",
      "first-page": "3688",
      "DOI": "10.1063/1.440733",
      "volume": "73",
      "year": "1980",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r85"
    },
    {
      "key": "2024021007313311600_r86"
    },
    {
      "key": "2024021007313311600_r87"
    },
    {
      "key": "2024021007313311600_r88"
    },
    {
      "key": "2024021007313311600_r89",
      "doi-asserted-by": "crossref",
      "first-page": "1138",
      "DOI": "10.1063/1.449476",
      "volume": "83",
      "year": "1985",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r90",
      "doi-asserted-by": "crossref",
      "first-page": "5188",
      "DOI": "10.1021/j100270a014",
      "volume": "89",
      "year": "1985",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024021007313311600_r91",
      "doi-asserted-by": "crossref",
      "first-page": "3711",
      "DOI": "10.1021/j100324a007",
      "volume": "92",
      "year": "1988",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024021007313311600_r92",
      "doi-asserted-by": "crossref",
      "first-page": "2700",
      "DOI": "10.1063/1.440484",
      "volume": "73",
      "year": "1980",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r93",
      "doi-asserted-by": "crossref",
      "first-page": "281",
      "DOI": "10.1063/1.1731099",
      "volume": "33",
      "year": "1960",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r94",
      "doi-asserted-by": "crossref",
      "first-page": "2959",
      "DOI": "10.1063/1.436049",
      "volume": "68",
      "year": "1978",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r95",
      "doi-asserted-by": "crossref",
      "first-page": "49",
      "DOI": "10.1007/BF01010840",
      "volume": "42",
      "year": "1986",
      "journal-title": "J. Stat. Phys."
    },
    {
      "key": "2024021007313311600_r96"
    },
    {
      "key": "2024021007313311600_r97",
      "doi-asserted-by": "crossref",
      "first-page": "3261",
      "DOI": "10.1021/j100322a038",
      "volume": "92",
      "year": "1988",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024021007313311600_r98",
      "doi-asserted-by": "crossref",
      "first-page": "1842",
      "DOI": "10.1063/1.1677461",
      "volume": "56",
      "year": "1972",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r99",
      "doi-asserted-by": "crossref",
      "first-page": "1903",
      "DOI": "10.1063/1.435917",
      "volume": "68",
      "year": "1978",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r100"
    },
    {
      "key": "2024021007313311600_r101"
    },
    {
      "key": "2024021007313311600_r102"
    },
    {
      "key": "2024021007313311600_r103"
    },
    {
      "key": "2024021007313311600_r104"
    },
    {
      "key": "2024021007313311600_r104a",
      "doi-asserted-by": "crossref",
      "first-page": "3342",
      "DOI": "10.1063/1.450956",
      "volume": "85",
      "year": "1986",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r104b",
      "doi-asserted-by": "crossref",
      "first-page": "6128",
      "DOI": "10.1063/1.453487",
      "volume": "87",
      "year": "1987",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r105"
    },
    {
      "key": "2024021007313311600_r105a",
      "doi-asserted-by": "crossref",
      "first-page": "476",
      "DOI": "10.1016/0009-2614(85)80084-1",
      "volume": "113",
      "year": "1985",
      "journal-title": "Chem. Phys. Lett."
    },
    {
      "key": "2024021007313311600_r106"
    },
    {
      "key": "2024021007313311600_r107",
      "doi-asserted-by": "crossref",
      "first-page": "4465",
      "DOI": "10.1063/1.441634",
      "volume": "74",
      "year": "1981",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r107a",
      "doi-asserted-by": "crossref",
      "first-page": "2191",
      "DOI": "10.1063/1.442331",
      "volume": "75",
      "year": "1981",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r108",
      "doi-asserted-by": "crossref",
      "first-page": "1295",
      "DOI": "10.1063/1.443951",
      "volume": "77",
      "year": "1982",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r109",
      "doi-asserted-by": "crossref",
      "first-page": "1788",
      "DOI": "10.1063/1.450425",
      "volume": "84",
      "year": "1986",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r110"
    },
    {
      "key": "2024021007313311600_r111",
      "doi-asserted-by": "crossref",
      "first-page": "2375",
      "DOI": "10.1063/1.446044",
      "volume": "79",
      "year": "1983",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r112"
    },
    {
      "key": "2024021007313311600_r113"
    },
    {
      "key": "2024021007313311600_r114"
    },
    {
      "key": "2024021007313311600_r115"
    },
    {
      "key": "2024021007313311600_r116",
      "doi-asserted-by": "crossref",
      "first-page": "105",
      "DOI": "10.1016/0378-4371(75)90162-4",
      "volume": "80",
      "year": "1975",
      "journal-title": "Physica A"
    },
    {
      "key": "2024021007313311600_r116a",
      "first-page": "425",
      "volume": "81",
      "year": "1975",
      "journal-title": "Physica A"
    },
    {
      "key": "2024021007313311600_r117",
      "doi-asserted-by": "crossref",
      "first-page": "3547",
      "DOI": "10.1063/1.1675379",
      "volume": "54",
      "year": "1971",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r118"
    },
    {
      "key": "2024021007313311600_r119",
      "doi-asserted-by": "crossref",
      "first-page": "376",
      "DOI": "10.1063/1.452574",
      "volume": "86",
      "year": "1987",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r120",
      "doi-asserted-by": "crossref",
      "first-page": "2049",
      "DOI": "10.1103/PhysRevA.3.2049",
      "volume": "3",
      "year": "1971",
      "journal-title": "Phys. Rev. A"
    },
    {
      "key": "2024021007313311600_r121",
      "doi-asserted-by": "crossref",
      "first-page": "149",
      "DOI": "10.1007/BF01010844",
      "volume": "42",
      "year": "1986",
      "journal-title": "J. Stat. Phys."
    },
    {
      "key": "2024021007313311600_r122"
    },
    {
      "key": "2024021007313311600_r122a",
      "doi-asserted-by": "crossref",
      "first-page": "5879",
      "DOI": "10.1063/1.442038",
      "volume": "75",
      "year": "1981",
      "journal-title": "J. Chem. Phys."
    },
    {
      "key": "2024021007313311600_r123",
      "doi-asserted-by": "crossref",
      "first-page": "4995",
      "DOI": "10.1021/j100303a019",
      "volume": "91",
      "year": "1987",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024021007313311600_r124",
      "doi-asserted-by": "crossref",
      "first-page": "4181",
      "DOI": "10.1021/j100266a008",
      "volume": "89",
      "year": "1985",
      "journal-title": "J. Phys. Chem."
    },
    {
      "key": "2024021007313311600_r125",
      "doi-asserted-by": "crossref",
      "first-page": "2513",
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