Voronoi deformation density (VDD) charges: Assessment of the Mulliken, Bader, Hirshfeld, Weinhold, and VDD methods for charge analysis

Journal of Computational Chemistry - Tập 25 Số 2 - Trang 189-210 - 2004
Célia Fonseca Guerra1, Jan‐Willem Handgraaf1, Evert Jan Baerends1, F. Matthias Bickelhaupt1
1Afdeling Theoretische Chemie, Scheikundig Laboratorium der Vrije Universiteit, De Boelelaan 1083, NL‐1081 HV Amsterdam, The Netherlands.

Tóm tắt

AbstractWe present the Voronoi Deformation Density (VDD) method for computing atomic charges. The VDD method does not explicitly use the basis functions but calculates the amount of electronic density that flows to or from a certain atom due to bond formation by spatial integration of the deformation density over the atomic Voronoi cell. We compare our method to the well‐known Mulliken, Hirshfeld, Bader, and Weinhold [Natural Population Analysis (NPA)] charges for a variety of biological, organic, and inorganic molecules. The Mulliken charges are (again) shown to be useless due to heavy basis set dependency, and the Bader charges (and often also the NPA charges) are not realistic, yielding too extreme values that suggest much ionic character even in the case of covalent bonds. The Hirshfeld and VDD charges, which prove to be numerically very similar, are to be recommended because they yield chemically meaningful charges. We stress the need to use spatial integration over an atomic domain to get rid of basis set dependency, and the need to integrate the deformation density in order to obtain a realistic picture of the charge rearrangement upon bonding. An asset of the VDD charges is the transparency of the approach owing to the simple geometric partitioning of space. The deformation density based charges prove to conform to chemical experience. © 2003 Wiley Periodicals, Inc. J Comput Chem 25: 189–210, 2004

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Tài liệu tham khảo

10.1063/1.1740588

10.1063/1.1740589

10.1063/1.1741876

10.1063/1.1741877

10.1021/om950966x

10.1039/f29878301307

10.1016/0009-2614(71)80561-4

10.1063/1.458812

10.1063/1.449486

10.1021/cr00088a005

10.1007/BF00549096

Bader R. F. W., 1990, Atoms in Molecules. A Quantum Theory, 10.1093/oso/9780198551683.001.0001

10.1002/jcc.540141213

10.1016/S1380-7323(96)80103-8

10.1021/jp0008694

10.1021/jp984777e

10.1021/jp980574e

10.1021/jp003345c

10.1002/9780470125823.ch3

10.1007/BF01122431

10.1007/BF01113058

10.1016/S0009-2614(00)00585-6

10.1002/jcc.10067

10.1002/qua.560290320

10.1021/j100084a048

10.1002/1096-987X(20010115)22:1<79::AID-JCC8>3.0.CO;2-B

10.1021/ja00204a001

10.1021/ja00167a012

10.1002/jcc.540080616

10.1002/jcc.540110311

Ferenzy G. G., 1991, J Comput Chem, 12, 913, 10.1002/jcc.540120802

10.1021/j100127a011

10.1002/jcc.540160204

10.1002/jcc.540150505

10.1002/jcc.540140905

10.1021/jp972682r

10.1007/BF00569246

10.1515/crll.1908.134.198

10.1021/ja00725a011

10.1016/0009-2614(71)80081-7

10.1007/BF00526433

10.1016/S0166-1280(00)00692-8

10.1002/jcc.1056

Fonseca Guerra C., 1995, Methods and Techniques for Computational Chemistry, 305

10.1016/0301-0104(73)80059-X

10.1016/0301-0104(75)80152-2

Baerends E. J., 1978, Int J Quantum Chem Symp, 12, 169

10.1007/s002140050021

10.1002/qua.560330204

10.1016/0021-9991(92)90277-6

10.1016/0092-640X(81)90004-8

Krijn J., 1984, Fit‐Functions in the HFS‐Method; Internal Report (in Dutch)

10.1063/1.454603

Slater J. C., 1974

10.1063/1.450025

10.1103/PhysRevA.38.3098

10.1139/p80-159

10.1103/PhysRevB.33.8822

10.1103/PhysRevB.34.7406

10.1063/1.460444

Ortiz C., Universitat Rovira i Virgili

B. J. Deppmeier A. J. Driessen T. S. Hehre W. J. Hehre J. A. Johnson P. E. Klunzinger J. M. Leonard I. N. Pham W. J. Pietro J. Yu Wavefunction Inc. Irvine CA

10.1021/ja00207a003

10.1021/ja992866e

10.1021/ja9928677

Allen L. C., 1998, 835

10.1002/(SICI)1521-3765(19991203)5:12<3581::AID-CHEM3581>3.0.CO;2-Y

10.1002/(SICI)1521-3757(19991004)111:19<3120::AID-ANGE3120>3.0.CO;2-D

10.1002/(SICI)1521-3773(19991004)38:19<2942::AID-ANIE2942>3.0.CO;2-V

10.1021/ja993262d

10.1021/cg010034y

10.1002/1521-3757(20020617)114:12<2194::AID-ANGE2194>3.0.CO;2-4

10.1002/1521-3773(20020617)41:12<2092::AID-ANIE2092>3.0.CO;2-M

10.1063/1.1592494

Bickelhaupt F. M., 2000, 1

10.1063/1.1676210

10.1002/qua.560100211

10.1021/ic50197a006

10.1021/ic50196a034

10.1007/BF02401406

Bickelhaupt F. M., 1998, New J Chem, 1, 10.1039/a708295i

10.1021/ic970897

10.1021/j100401a010

10.1071/PH850273

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Journal of Computational Chemistry

Tập 25 Số 2

189-210

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