DOI: 10.1063/1.474671. A new definition of cavities for the computation of solvation free energies by the polarizable continuum model

A new definition of cavities for the computation of solvation free energies by the polarizable continuum model

10.1063/1.474671

Crossref journal-article

AIP Publishing

The Journal of Chemical Physics (317)

Abstract

A set of rules for determining the atomic radii of spheres used to build the molecular cavities in continuum solvation models are presented. The procedure is applied to compute the hydration free energy for molecules containing H, C, N, O, F, P, S, Cl, Br, and I at a computational level (Hartree–Fock with a medium size basis set) allowing the study of relatively large systems. The optimized radii reduce the mean error with respect to the experimental solvation energies below 0.20 kcal/mol for a set of 43 neutral solutes and around 1 kcal/mol for 27 ions. Moreover the correct trends are observed for the solvation energies of homolog series, like the series ammonia–trimethylamine, that are not correctly reproduced by usual solvation models.

Bibliography

Barone, V., Cossi, M., & Tomasi, J. (1997). A new definition of cavities for the computation of solvation free energies by the polarizable continuum model. The Journal of Chemical Physics, 107(8), 3210â3221.

Authors 3

Vincenzo Barone (first)
Maurizio Cossi (additional)
Jacopo Tomasi (additional)

References 40 Referenced 2,233

10.1021/cr00031a013 / Chem. Rev. (1994)
{'key': '2024020600332964200_r1a'}
10.1016/0301-0104(81)85090-2 / Chem. Phys. (1981)
10.1016/0009-2614(96)00349-1 / Chem. Phys. Lett. (1996)
10.1002/(SICI)1096-987X(199605)17:7<806::AID-JCC5>3.0.CO;2-W / J. Comput. Chem. (1996)
{'key': '2024020600332964200_r5', 'first-page': '16', 'volume': '100', 'year': '1996', 'journal-title': 'J. Phys. Chem.'} / J. Phys. Chem. (1996)
10.1016/0301-0104(89)85013-X / Chem. Phys. (1989)
{'key': '2024020600332964200_r7', 'first-page': '327', 'volume': '225', 'year': '1996', 'journal-title': 'Chem. Phys. Lett.'} / Chem. Phys. Lett. (1996)
{'key': '2024020600332964200_r8', 'first-page': '16', 'volume': '100', 'year': '1996', 'journal-title': 'J. Phys. Chem.'} / J. Phys. Chem. (1996)
{'key': '2024020600332964200_r9', 'first-page': '14', 'volume': '99', 'year': '1995', 'journal-title': 'J. Phys. Chem.'} / J. Phys. Chem. (1995)
10.1063/1.460205 / J. Chem. Phys. (1991)
{'key': '2024020600332964200_r11'}
{'key': '2024020600332964200_r12'}
10.1007/BF00533485 / Theor. Chim. Acta (1973)
10.1021/ja953665n / J. Am. Chem. Soc. (1996)
{'key': '2024020600332964200_r15', 'first-page': '295', 'volume': '4', 'year': '1983', 'journal-title': 'J. Comput. Chem.'} / J. Comput. Chem. (1983)
{'key': '2024020600332964200_r16', 'first-page': '695', 'volume': '29', 'year': '1995', 'journal-title': 'Int. J. Quantum Chem. Quantum Chem. Symp.'} / Int. J. Quantum Chem. Quantum Chem. Symp. (1995)
10.1002/jcc.540100504 / J. Comput. Chem. (1989)
10.1002/jcc.540120703 / J. Comput. Chem. (1991)
10.1002/(SICI)1096-987X(19960115)17:1<57::AID-JCC6>3.0.CO;2-# / J. Comput. Chem. (1996)
10.1063/1.466842 / J. Chem. Phys. (1994)
10.1107/S0567740878010638 / Acta Crystallogr. B (1978)
10.1021/cr60304a002 / Chem. Rev. (1976)
10.1063/1.472829 / J. Chem. Phys. (1996)
10.1063/1.473558 / J. Chem. Phys. (1997)
10.1063/1.471208 / J. Chem. Phys. (1996)
10.1002/jcc.540151009 / J. Comput. Chem. (1994)
10.1021/j100785a001 / J. Phys. Chem. (1964)
{'key': '2024020600332964200_r27'}
{'key': '2024020600332964200_r28', 'first-page': '237', 'volume': '15', 'year': '1994', 'journal-title': 'J. Comput. Chem.'} / J. Comput. Chem. (1994)
10.1016/0301-0104(94)00029-8 / Chem. Phys. (1994)
10.1007/BF00646936 / J. Sol. Chem. (1981)
10.1021/ja00280a002 / J. Am. Chem. Soc. (1986)
10.1002/ijch.199300049 / Isr. J. Chem. (1993)
{'key': '2024020600332964200_r33', 'first-page': '403', 'volume': '30', 'year': '1996', 'journal-title': 'Int. J. Quantum Chem. Quantum Chem. Symp.'} / Int. J. Quantum Chem. Quantum Chem. Symp. (1996)
{'key': '2024020600332964200_r34', 'first-page': '11', 'volume': '100', 'year': '1996', 'journal-title': 'J. Phys. Chem.'} / J. Phys. Chem. (1996)
{'key': '2024020600332964200_r35', 'first-page': '11', 'volume': '116', 'year': '1994', 'journal-title': 'J. Am. Chem. Soc.'} / J. Am. Chem. Soc. (1994)
{'key': '2024020600332964200_r36'}
10.1021/ja00088a027 / J. Am. Chem. Soc. (1994)
{'key': '2024020600332964200_r38', 'first-page': '16', 'volume': '100', 'year': '1996', 'journal-title': 'J. Phys. Chem.'} / J. Phys. Chem. (1996)

Dates

Type	When
Created	23 years, 1 month ago (July 26, 2002, 8:25 a.m.)
Deposited	1 year, 6 months ago (Feb. 5, 2024, 7:52 p.m.)
Indexed	1 week, 3 days ago (Aug. 19, 2025, 6:21 a.m.)
Issued	28 years ago (Aug. 22, 1997)
Published	28 years ago (Aug. 22, 1997)
Published Print	28 years ago (Aug. 22, 1997)

Funders 0

None

BibTeX

@article{Barone_1997, title={A new definition of cavities for the computation of solvation free energies by the polarizable continuum model}, volume={107}, ISSN={1089-7690}, url={http://dx.doi.org/10.1063/1.474671}, DOI={10.1063/1.474671}, number={8}, journal={The Journal of Chemical Physics}, publisher={AIP Publishing}, author={Barone, Vincenzo and Cossi, Maurizio and Tomasi, Jacopo}, year={1997}, month=aug, pages={3210–3221} }

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