New XDM-corrected potential energy surfaces for Ar–NO(X{sup 2}Π): A comparison with CCSD(T) calculations and experiments
- Chemical Physics Program, University of Maryland, College Park, Maryland 20742 (United States)
- Department of Chemistry and Biochemistry, University of Maryland, College Park, Maryland 20742 (United States)
We report new potential energy surfaces for the ground state Ar–NO(X{sup 2}Π) van der Waals system calculated using the unrestricted Hartree-Fock (UHF) method with the addition of the Becke-Roussel correlation functional and exchange-hole dipole moment dispersion correction (XDM). We compare UHFBR-XDM surfaces and those previously reported by Alexander from coupled cluster CCSD(T) calculations [J. Chem. Phys. 111, 7426 (1999)]. The bound states of Ar–NO have been investigated with these new UHFBR-XDM surfaces, including relative energy-level spacing, adiabatic bender states and wave functions, and spectroscopic data. These results have been found to be in good agreement with calculations based on the CCSD(T) PESs. These new PESs are used to investigate the inelastic scattering of NO(X) by Ar. Full close-coupling integral cross sections at collision energies of 442 cm{sup −1}, 1774 cm{sup −1} and differential cross sections at collision energy of 530 cm{sup −1} were determined for transitions out of the lowest NO(X) rotational level (j = ω = 1/2,f). These cross sections are in good agreement with those calculated with CCSD(T) and accordingly in good agreement with the most recent initial and final state resolved experimental data. The UHFBR-XDM scheme yields high-quality potential surfaces with computational cost comparable to the Hartree-Fock method and our results may serve as a benchmark for application of this scheme to collisions between larger molecules.
- OSTI ID:
- 22415827
- Journal Information:
- Journal of Chemical Physics, Vol. 142, Issue 2; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA); ISSN 0021-9606
- Country of Publication:
- United States
- Language:
- English
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Related Subjects
BENCHMARKS
BOUND STATE
COMPARATIVE EVALUATIONS
CORRECTIONS
COUPLING
DIFFERENTIAL CROSS SECTIONS
DIPOLE MOMENTS
GROUND STATES
HARTREE-FOCK METHOD
HOLES
INELASTIC SCATTERING
INTEGRAL CROSS SECTIONS
MOLECULE COLLISIONS
MOLECULES
NITRIC OXIDE
POTENTIAL ENERGY
POTENTIALS
SURFACES
VAN DER WAALS FORCES