Skip to main content
OSTI.GOVU.S. Department of Energy Office of Scientific and Technical Information
U.S. Department of Energy
Office of Scientific and Technical Information
 

Energy Decomposition Analysis for Interactions of Radicals: Theory and Implementation at the MP2 Level with Application to Hydration of Halogenated Benzene Cations and Complexes between CO2-· and Pyridine and Imidazole

Journal Article · · Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory
 [1];  [1];  [1];  [1];  [1];  [1];  [2];  [1]
  1. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry
  2. Univ. of California, Berkeley, CA (United States). Dept. of Chemistry and Dept. of Bioengineering
+ Show Author Affiliations
To study intermolecular interactions involving radicals at the correlated level, the energy decomposition analysis scheme for second-order Møller-Plesset perturbation theory based on absolutely localized molecular orbitals (ALMO-MP2-EDA) is generalized to unrestricted and restricted open-shell MP2. The benefit of restricted open-shell MP2 is that it can provide accurate binding energies for radical complexes where density functional theory can be error-prone due to delocalization errors. As a model application, the open-shell ALMO-MP2-EDA is applied to study the first solvation step of halogenated benzene radical cations, where both halogen- and hydrogen-bonded isomers are possible. We determine that the lighter halogens favor the hydrogen-bonded form, while the iodine-substituted species prefers halogen bonding due to larger polarizability and charge transfer at the halogen. As a second application, relevant to the activation of CO2 in photoelectrocatalysis, complexes of CO2-· interacting with both pyridine and imidazole are analyzed with ALMO-MP2-EDA. The results reveal the importance of charge transfer into the π* orbital of the heterocycle in controlling the stability of the carbamate binding mode, which is favored for pyridine but not for imidazole.
Research Organization:
Lawrence Berkeley National Laboratory (LBNL), Berkeley, CA (United States)
Sponsoring Organization:
National Science Foundation (NSF); USDOE Office of Science (SC)
Grant/Contract Number:
AC02-05CH11231
OSTI ID:
1605260
Journal Information:
Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory, Journal Name: Journal of Physical Chemistry. A, Molecules, Spectroscopy, Kinetics, Environment, and General Theory Journal Issue: 44 Vol. 123; ISSN 1089-5639
Publisher:
American Chemical SocietyCopyright Statement
Country of Publication:
United States
Language:
English

Figures / Tables (12)

Figure 1(p. 7)figure Figure 1
Figure 2(p. 15)figure Figure 2
Table 1(p. 18)table Table 1
Figure 3(p. 20)figure Figure 3
Figure 4(p. 20)figure Figure 4
Figure 5(p. 21)figure Figure 5
Figure 6(p. 22)figure Figure 6
Figure 7(p. 23)figure Figure 7
Figure 8(p. 24)figure Figure 8
Figure 9(p. 26)figure Figure 9
Figure 10(p. 27)figure Figure 10
Figure 11(p. 28)figure Figure 11

Similar Records

An energy decomposition analysis for second-order Møller–Plesset perturbation theory based on absolutely localized molecular orbitals
Journal Article · Fri Aug 28 00:00:00 EDT 2015 · Journal of Chemical Physics · OSTI ID:22493571

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY