Journal
JOURNAL OF PHYSICAL CHEMISTRY LETTERS
Volume 5, Issue 8, Pages 1380-1385Publisher
AMER CHEMICAL SOC
DOI: 10.1021/jz500165u
Keywords
-
Categories
Funding
- LDRD grant, Lawrence Berkeley National Laboratory
- U.S. Department of Energy, Office of Basic Energy Sciences, Division of Chemical Sciences, Geosciences and Biosciences [DE-FG02-12ER16362]
Ask authors/readers for more resources
The electron-electron correlation energy is negative, and attractive dispersion interactions are entirely a correlation effect; therefore, the contribution of correlation to intermolecular binding is commonly assumed to be negative, or binding in nature. However, there are many cases where the long-range correlation binding energy is positive, with certain geometries of the water dimer as a prominent example. Geometries with dipoles misaligned can also have an electrostatically dominated, though negative, long-range correlation binding. In either case, the interaction decays as R-3. This has its origin in the systematic overestimation of dipole moments by Hartree-Fock theory, leading to a reduction in the calculated electrostatic attraction upon inclusion of correlation. Thus, energy decomposition analyses that include correlation but do not correct mean field electrostatic terms are suboptimal. Attenuated second-order Moller-Plesset theory, which smoothly truncates long-range electron correlation effects to zero, can, paradoxically, have the correct long-range behavior for many intermolecular interactions.
Authors
I am an author on this paper
Click your name to claim this paper and add it to your profile.
Reviews
Recommended
No Data Available