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Comparative density functional theory and post-Hartree-Fock (CCSD, CASSCF) studies on the electronic structure of halogen nitrites ClONO and BrONO using quantum chemical topology
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10.1063/1.3624894
/content/aip/journal/jcp/135/9/10.1063/1.3624894
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/9/10.1063/1.3624894

Figures

Image of FIG. 1.
FIG. 1.

Optimized geometrical structures of cis- and trans- XONO (X=Cl, Br).

Image of FIG. 2.
FIG. 2.

Comparison of the electron density ρ(r) values and the electron density Laplacian values 2 ρ(r) for (3,−1) CP, localized for the X–O bond in cis- and trans-XONO (X=F, Cl, Br, I).

Image of FIG. 3.
FIG. 3.

2D-plot of the electron localization function (ELF) for cis-ClONO with marked positions of core and valence attractors and schematic Lewis bonds. Calculations have been performed at the CCSD/aug-cc-pVTZ//CCSD(T)/aug-cc-pVTZ level. The picture is viewed along a molecular plane.

Image of FIG. 4.
FIG. 4.

2D and 3D-plots of the electron localization function (ELF) for trans-ClONO with marked positions of core and valence attractors and schematic Lewis bonds. Calculations performed at the CCSD/aug-cc-pVTZ//CCSD(T)/aug-cc-pVTZ level. The picture is presented for molecular plane. At 3D-plots the basin populations are presented.

Image of FIG. 5.
FIG. 5.

(a) Superimposition of 2D (molecular plane) and 3D (core regions) representations of the localized electron detector (LED) function for cis-ClONO. Calculations at the CASSCF(14,12)/aug-cc-pVTZ//CCSD(T)/aug-cc-pVTZ level. (b) Superimposition of 3D representations of the localized electron detector (LED) function for cis-ClONO. The core regions (solid black) are represented for LED=3.7 and the valence regions (black points) for LED=0.7. Calculations at the CASSCF(14,12)/aug-cc-pVTZ//CCSD(T)/aug-cc-pVTZ level.

Image of FIG. 6.
FIG. 6.

(a) Superimposition of 2D (molecular plane) and 3D (core regions) representations of the localized electron detector (LED) function for trans-ClONO. Calculations at the CASSCF(14,12)/aug-cc-pVTZ//CCSD(T)/aug-cc-pVTZ level. (b) A superimposition of 3D representations of the localized electron detector (LED) function for trans-ClONO. The core regions (solid black) are represented for LED=2.18 and valence regions (black points) for LED being in range between 0.03 and 2.18. Calculations at the CASSCF(14,12)/aug-cc-pVTZ//CCSD(T)/aug-cc-pVTZ level.

Image of FIG. 7.
FIG. 7.

Evolution of total energy and mean electron population () for the V(Br,O1) bonding basin in trans-BrO1NO2 for the dissociation of the Br–O1 bond. Calculations at B3LYP/aug-cc-pVTZ level.

Image of FIG. 8.
FIG. 8.

A dissociation of the N–O1 bond in trans-Br–O1–N=O2. An evolution of the total energy and mean electron population () for the basin characterizing the N–O1 bond. Calculations at B3LYP/aug-cc-pVTZ level. (b) Dissociation of the N–O1 bond in cis-Br–O1–N=O2. Evolution of total energy and mean electron population () for the basin characterizing the N–O1 bond. Calculations at B3LYP/aug-cc-pVTZ level.

Tables

Generic image for table
Table I.

The optimized geometrical parameters of ClONO and BrONO. The Cs point group of symmetry.

Generic image for table
Table II.

The total energy difference (ΔE) [kJ/mol] calculated between the trans- and cis-isomers (E tot cisE tot trans) corrected by the zero-point energy difference (ΔE + ΔZPVE).

Generic image for table
Table III.

Summary of NPA and NBO analysis for cis- and trans-XO1NO2 (X=Cl, Br) performed at the B3LYP/aug-cc-pVTZ level. The core and lone pairs of X atom have been omitted.The contribution of d orbitals is less than 1% and has been omitted.

Generic image for table
Table IV.

Results of perturbative analysis of NBO donor-acceptor interactions for cis- and trans-XONO (X=Cl, Br) performed at the B3LYP/aug-cc-pVTZ level. Only second-order energy lowerings larger than 42 kJ/mol (10 kcal/mol) are presented and mixing with Rydberg orbitals has been omitted.

Generic image for table
Table V.

The topological data calculated from topological analysis of the electron density field (AIM) at the CCSD/aug-cc-pVTZ//CCSD(T)/aug-cc-pVTZ level for Cl–O1–N=O2 and Br–O1–N=O2 molecules.

Generic image for table
Table VI.

The basin populations (e) calculated from topological analysis of the ELF field at the CCSD/aug-cc-pVTZ//CCSD(T)/aug-cc-pVTZ level for Cl–O1–N=O2 and Br–O1–N=O2 molecules.

Generic image for table
Table VII.

The N and O1 atomic contributions [e] to ELF-basins of the N–O1 bond in cis- and trans-isomers of Cl–O1–N=O2 and Br–O1–N=O2 calculated at the CCSD/aug-cc-pVTZ//CCSD(T)/aug-cc-pVTZ level.

Generic image for table
Table VIII.

The basin populations calculated for the X–O1, O1–N, and N=O2 bonds in cis- and trans-isomers of Cl–O1–N=O2 and Br–O1–N=O2 from topological analysis of the ELI-D field at CASSCF(14,12)/aug-cc-pVTZ//CCSD(T)/aug-cc-pVTZ level.

Generic image for table
Table IX.

The fragmentation energies (kJ/mol) for cis-XONO(1A) X=Cl, Br.

Generic image for table
Table X.

The bond length and topological data calculated from topological analysis of the electron density and electron localization function fields at the B3LYP/aug-cc-pVTZ level for Cl–O1–N=O2 and Br–O1–N=O2 molecules.

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/content/aip/journal/jcp/135/9/10.1063/1.3624894
2011-09-01
2014-04-16
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Scitation: Comparative density functional theory and post-Hartree-Fock (CCSD, CASSCF) studies on the electronic structure of halogen nitrites ClONO and BrONO using quantum chemical topology
http://aip.metastore.ingenta.com/content/aip/journal/jcp/135/9/10.1063/1.3624894
10.1063/1.3624894
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