DOI: 10.1002/jcc.540110311. Determining atom‐centered monopoles from molecular electrostatic potentials. The need for high sampling density in formamide conformational analysis

Determining atom‐centered monopoles from molecular electrostatic potentials. The need for high sampling density in formamide conformational analysis

10.1002/jcc.540110311

Crossref journal-article

Wiley

Journal of Computational Chemistry (311)

Abstract

AbstractAn improved method for computing potential‐derived charges is described which is based upon the CHELP program available from QCPE.1 This approach (CHELPG) is shown to be considerably less dependent upon molecular orientation than the original CHELP program. In the second part of this work, the CHELPG point selection algorithm was used to analyze the changes in the potential‐derived charges in formamide during rotation about the CN bond. In order to achieve a level of rotational invariance less than 10% of the magnitude of the electronic effects studied, an equally‐spaced array of points 0.3 Å apart was required. Points found to be greater than 2.8 Å from any nucleus were eliminated, along with all points contained within the defined VDW distances from each of the atoms. The results are compared to those obtained by using CHELP. Even when large numbers of points (ca. 3000) were sampled using the CHELP selection routine, the results did not indicate a satisfactory level of rotatational invariance. On the basis of these results, the original CHELP program was found to be inadequate for analyzing internal rotations.

Bibliography

Breneman, C. M., & Wiberg, K. B. (1990). Determining atomâcentered monopoles from molecular electrostatic potentials. The need for high sampling density in formamide conformational analysis. Journal of Computational Chemistry, 11(3), 361â373. Portico.

Authors 2

Curt M. Breneman (first)
Kenneth B. Wiberg (additional)

References 23 Referenced 4,321

10.1002/jcc.540080616
10.1016/S0065-3276(08)60236-1
For example the AMBER force‐field uses a point‐charge approximation of electrostatic interactions. See:
10.1002/jcc.540020311 / J. Comp. Chem. by Wiener P. K. (1981)
10.1002/jcc.540030306
10.1021/ja00368a004
10.1021/j100494a019
10.1080/00268977900100431
{'key': 'e_1_2_1_8_2', 'first-page': '5', 'volume': '1984', 'author': 'Singh U. C.', 'journal-title': 'J. Comp. Chem.'} / J. Comp. Chem. by Singh U. C.
The PDM88 program (QCPE) can fit an atom (and bond)‐centered multipole series to the molecular electrostatic potential. See:
10.1002/jcc.540090705
10.1002/jcc.540020312
M.Connolly QCPE Program429 (1982). (10.1017/S0007125000111675)
The sizes of the “small” exclusion radii were selected on the basis of electron density considerations using the standard values in reference 1 as a guide. The “large” radii were chosen as an arbitrary distance that would always be outside of regions where local changes in electrostatic potential are large.
The results in Table IX and Figures 1–4 are presented in the reverse order for clarity.
The mode‐walking was done using the EF modewalk algorithm incorporated in Gaussian90.
10.1016/0022-2852(74)90274-4
The electrostatic potential minima were located using the automated search procedure in Gaussian88/90.
10.1021/ja00254a006
C. M.BrenemanandK. B.Wiberg manuscript in preparation.
{'key': 'e_1_2_1_19_2', 'volume-title': 'Structure and Reactivity', 'author': 'Greenberg A.', 'year': '1987'} / Structure and Reactivity by Greenberg A. (1987)
{'key': 'e_1_2_1_20_2', 'volume-title': 'Gaussian86', 'author': 'Frisch M. J.', 'year': '1984'} / Gaussian86 by Frisch M. J. (1984)
{'key': 'e_1_2_1_21_2', 'volume-title': 'Gaussian90', 'author': 'Frisch M. J.', 'year': '1988'} / Gaussian90 by Frisch M. J. (1988)

Dates

Type	When
Created	20 years, 7 months ago (Jan. 1, 2005, 7:31 p.m.)
Deposited	1 year, 9 months ago (Oct. 22, 2023, 7:09 a.m.)
Indexed	8 hours, 51 minutes ago (Aug. 21, 2025, 1:14 p.m.)
Issued	35 years, 4 months ago (April 1, 1990)
Published	35 years, 4 months ago (April 1, 1990)
Published Online	20 years, 11 months ago (Sept. 7, 2004)
Published Print	35 years, 4 months ago (April 1, 1990)

Funders 0

None

BibTeX

@article{Breneman_1990, title={Determining atom‐centered monopoles from molecular electrostatic potentials. The need for high sampling density in formamide conformational analysis}, volume={11}, ISSN={1096-987X}, url={http://dx.doi.org/10.1002/jcc.540110311}, DOI={10.1002/jcc.540110311}, number={3}, journal={Journal of Computational Chemistry}, publisher={Wiley}, author={Breneman, Curt M. and Wiberg, Kenneth B.}, year={1990}, month=apr, pages={361–373} }

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