James Harrison

Quantum Chemistry

Emeritus Professor



Research webpage

Primary Research Area

Theoretical and Computational (Th)

Other Area(s) of Interest

Chemical Physics (CP)

Physical (Ph)


Advances in fundamental theory and computer technology enable us to construct wavefunctions for atoms and molecules which are of unprecedented ac­curacy. We use these functions to assist in the interpretation of spectroscopic experiments and to develop and refine the qualitative notions of chemical bonding. Our current focus is to understand:

Electron density map of the 1+ state of HCl
calculated using a CASSCF wavefunction and
the vqz basis set.

The electronic structure of the ground and low-lying states of small molecules containing a transition metal atom. Diatomics of interest include MX where M is a transition metal (Sc to Zn) and X is a main group element (H to Cl). These molecules are of great interest as models for the nature of the transition meta-main group element chemical bond. Triatomics include the metal hydroxides MOH & HMO and the carbynes MCH, the understanding of which is fundamental to the reactions of transition metals with hydrocarbons. We are also interested in the structure of the mono- and dipositive ions of these systems.

Molecular quadrupole moments
as a function of bond length.

The nature of molecular multipole moments and the information contained in these moments about the chemical bond. While we all have an instinctive feeling about the meaning of a molecular dipole moment and how it reflects the charge distribution in a molecule the same instincts often fail when considering for example, the quadrupole moment. Some of this problem is that the quadrupole moment is a second rank tensor while the dipole moment is a tensor of the first rank. However even for homonuclear diatomics where the quadrupole tensor has only one unique component the relationship between this component and the molecular charge density is not well understood. We have recently shown that the molecular quadrupole moment can be written as the sum of the quadrupole moments of the constituent atoms plus a term that depends on the shift in the electron density upon bond formation. In the course of this work we have defined the quadrupole moment density that shows where in the molecule the molecular contribution to the quadrupole moment comes from. We are extending these ideas to other one electron properties like the electric field gradient at a particular nucleus and the dipole moment (still more to learn!).

The spatial distribution of electron spin in open shell molecules. We have recently shown in the open shell nitrogen halides, NF, NCl and NBr that α and β spins flow in opposite directions as the chemical bond forms. We are exploring this observation and the role that electronegativity (chemical potential) plays.

Selected Publications

Electronic Structure of Diatomic Molecules Composed of a First-Row Transition Metal and Main-Group Element (H-F), J. F. Harrison, Chem. Rev. 2000, 100, 679-716.

Dipole and quadrupole moment functions of the hydrogen halides, HF, HCl, HBr, and HI: A Hirshfeld interpretation, J. F. Harrison, J. Chem. Phys. 2008, 128, 114320.

Collision-Induced dipoles and Polarizabilities of Pairs of Hydrogen Molecules: Ab Initio Calculations and Results from Spherical Tensor Analysis, X. Li, J. F. Harrison, M. Gustafsson, F. Wang, M. Abel, L. Frommhold, and K. L. C. Hunt, Proc. ICCMSE 2009.

A Hirshfeld interpretation of the charge, spin distribution, and polarity of the dipole moment of the open shell nitrogen halides: NF, NCl, and NBr, J. F. Harrison, J. Chem. Phys. 2009, 131, 044117.

“Methylene: A Personal Perspective”, James F. Harrison, pages 33-43, “Advances in the Theory of Atomic and Molecular Systems: Conceptual and Computational Advances in Quantum Chemistry” Edited by P. Piecuch, J. Maruani, G. Delgado-Barrio, and S. Wilson, Springer 2009.

Ab Initio Investigation of Titanium Hydroxide Isomers and their Cations, (H-Ti-O)+0 and (Ti-O-H)+0, Milordos E, Harrison J. F. and Hunt K. L. C, J. Chem. Phys. 2011, 135, 144111.

A Hirshfeld interpretation of the local moment composition of the quadrupole moments of the halogenated acetylenes FCCF, ClCCCl, BrCCBr, and ICCI, J. F. Harrison, Computational and Theoretical Chemistry 2012, 999, 83-88.

The ground and excited states of vanadium hydroxide isomers and their anions and cations, (V-OH)0+- and (H-V-O)0+-, Milordos E, Harrison J. F. and Hunt K. L. C., J. Chem. Phys. 2013, 138, 114305.

Hirshfeld density partitioning technique: A first application to the transition metal compounds, HScO, TiO and VO, Milordos E and Harrison J. F., J. Chem. Phys. 2013, 138, 184305-7.


B.S., 1962, Drexel Institute of Technology

M.A., 1964,Princeton Univ.

Ph.D., 1966, Princeton Univ.

NSF Postdoctoral Fellow, 1966-67, Research Associate, 1967-68, Indiana Univ.

Scientist in Residence, 1980-81Argonne National Laboratory.



2004 Member (XXXVI) Midwest Theoretical Chemistry Conference (Organizing committee)
2003 President Sigma Xi Honor Society (Michigan State University)
1995 Distinguished Faculty Award College of Natural Science
1992 Member (XXV) Midwest Theoretical Chemistry Conference (Organizing committee)
1986 - 1993 Associate Chair for undergraduate education MSU (Chemistry)
1982 Member (XV) Midwest Theoretical Chemistry Conference (Organizing committee)
1973 - 1974 Chairman ACS (MSU)
1972 Organizer (VI) Midwest Theoretical Chemistry Conference
1972 - 1977 Teacher-Scholar Award Camille and Henry Dreyfus Foundation
1972 - 1973 Secretary ACS (MSU)
1971 - 1972 Treasurer ACS (MSU)
1966 - 1967 Postdoctoral Fellow National Science Foundation
1966 Ph.D. Princeton University
1964 - 1966 National Aeronautics & Space Administration Fellow Princeton University
1964 M.A. Princeton University
1963 - 1964 American Machine & Foundary Fellow Princeton University
1962 Bachelor of Science Drexel Institute of Technology
1962 Scholastic Achievement Award Philadelphia ACS
1957 - 1962 Food Fair Scholarship Drexel Institute of Technology
Phi Kappa Phi
Alternate Councilor ACS (MSU)
Immediate Past Chairman ACS (MSU)
Councilor ACS (MSU)