“CHELPG”的意思、由来-开放百科全书

The charge calculation methods based on fitting of molecular electrostatic potential (MESP) (including CHELPG) are not well-suitable for the treatment of larger systems, where some of the innermost atoms are located far away from the points at which the MESP is computed. In such a situation, variations of the innermost atomic charges will not lead to significant changes of the MESP outside of the molecule, which means accurate values for the innermost atomic charges are not well-determined by the MESP outside of the molecule. This problem is solved by density derived electrostatic and chemical (DDEC) methods that partition the electron density cloud in order to provide chemically meaningful net atomic charges that approximately reproduce the electrostatic potential surrounding the material.^[4]

It should be remembered that atomic charges depend on the molecular conformation. The representative atomic charges for flexible molecules hence should be computed as average values over several molecular conformations.

A number of alternative MESP charge schemes have been developed, such as those employing Connolly surfaces^[5] or geodesic point selection^[6] algorithms, in order to improve rotational invariance by increasing the point selection density and reducing anisotropies in the sampled points on the MESP surface. While CHELPG is restricted to non-periodic (e.g., molecular) systems, the DDEC^[4] methods can be applied to both non-periodic and periodic materials.

CHELPG charges can be computed using the popular ab initio quantum chemical packages such as Gaussian, GAMESS-US and ORCA.

References

1. ^{{ cite journal | last1 = Breneman | first1 = Curt M. | last2 = Wiberg | first2 = Kenneth B. | title = Determining atom-centered monopoles from molecular electrostatic potentials. The need for high sampling density in formamide conformational analysis | journal = Journal of Computational Chemistry | volume = 11 | pages = 361 | year = 1990 | doi = 10.1002/jcc.540110311 | issue = 3}}
2. ^{{ cite book | url = http://www.wiley.com/WileyCDA/WileyTitle/productCd-0470011874.html | title = Introduction to Computational Chemistry | edition = 2nd | first = Frank | last = Jensen | publisher = Wiley | isbn = 978-0-470-01187-4 | access-date = 2009-02-20 | archive-url = https://web.archive.org/web/20081019081018/http://www.wiley.com/WileyCDA/WileyTitle/productCd-0470011874.html# | archive-date = 2008-10-19 | dead-url = yes | df = }}
3. ^{{ cite book | url = http://www.wiley.com/WileyCDA/WileyTitle/productCd-0470091827.html | title = Essentials of Computational Chemistry: Theories and Models |edition = 2nd | first = Christopher J. | last = Cramer |publisher = Wiley | isbn = 978-0-470-09182-1}}
4. ^¹{{cite journal | doi = 10.1039/c6ra04656h | journal = RSC Adv. | title = Introducing DDEC6 atomic population analysis: part 1. Charge partitioning theory and methodology | author1 = T. A. Manz | author2 = N. Gabaldon-Limas | year = 2016 | volume = 6 | pages = 47771–47801| url = https://zenodo.org/record/895508/files/article.pdf }}
5. ^{{ cite journal | last1 = Singh | first1 = U. Chandra | last2 = Kollman | first2 = Peter A. | title = An approach to computing electrostatic charges for molecules. | journal = Journal of Computational Chemistry | volume = 5 | issue = 2 | year = 1984 | pages = 129–145 | doi=10.1002/jcc.540050204}}
6. ^{{ cite journal | last1 = Spackman | first1 = Mark A. | title = Potential derived charges using a geodesic point selection scheme. | journal = Journal of Computational Chemistry | volume = 17 | issue = 1 | year = 1996 | pages = 1–18 | doi=10.1002/(sici)1096-987x(19960115)17:1<1::aid-jcc1>3.0.co;2-v}}