Na2O and Na2O+: Thermodynamics and low-lying electronic states
Soldan, P., Lee, E. P. F., Gamblin, S. D. and Wright, T. G. (2000) Na2O and Na2O+: Thermodynamics and low-lying electronic states. Journal of Physical Chemistry A, 104, (15), 3317-3325. (doi: 10.1021/jp994350n).
Download
Full text not available from this repository.
Description/Abstract
High-level [up to RCCSD(T)/aug-cc-pV5S'//RCCSD/aug-cc-pVQZ'] ab initio calculations are performed on Na2O and Na2O+ (where the 'indicates a nonstandard aug-cc-pVXZ basis set). The electronic groundstate equilibrium geometries are found to be linear in both cases. The heats of formation, Delta H-f(298)(Na2O) and Delta Hf-298(Na2O+), are derived, with the recommended values being Delta H-f(298)(Na2O) = -5.5 +/- 1.0 kcal mol(-1) and Delta H-f(298)(Na2O+) = 106.7 +/- 0.5 kcal mol(-1), respectively. It is found that large basis sets, the RCCSD(T) method, and appropriate account of basis set superposition error (BSSE) are necessary in order to obtain reliable results. S-298 for Na2O and Na2O+ are also calculated giving 67 and 63 cal K-1 mol(-1), respectively. The calculations also yield Delta H-a(298)(Na2O)= 115.5 +/- 1 kcal mol(-1) and Do(NaO Na) = 52 +/- 1 kcal mol(-1) The adiabatic ionization energy of Na2O is calculated as 4.86 +/- 0.02 eV and corresponds to the process Na2O+((XIIu)-I-2) + e(-) <-- Na2O(X(1)Sigma(g)(divided by)); the corresponding vertical ionization energy is calculated to be 5.00 +/- 0.02 eV. The ground state of Na2O+ is established as the (IIu)-I-2 state, with the A(2)Sigma(u)(+) state lying ca. 0.65 eV above. The low:lying triplet states of Na2O are briefly considered. The implication of the present results on the mass spectrometry of the vapor above Na2O is discussed.
| Item Type: | Article |
|---|---|
| Related URLs: | |
| Keywords: | alkaline-earth oxides, vaporization behavior, total energies, sodium-oxide, oxygen, heat, ionization, clusters, nao, g2 |
| Subjects: | Q Science Q Science > QD Chemistry |
| Divisions: | University Structure - Pre August 2011 > School of Chemistry |
| Item ID: | 18957 |
| Date Deposited: | 05 Jan 2006 |
| Last Modified: | 01 Jun 2011 01:46 |
| Contributors: | Soldan, P. (Author) Lee, E. P. F. (Author) Gamblin, S. D. (Author) Wright, T. G. (Author) |
| Date: | 20 April 2000 |
| Status: | Published |
| URI: | http://eprints.soton.ac.uk/id/eprint/18957 |
Actions (login required)
 |
View Item |
