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Title: Toward accurate thermochemistry of the {sup 24}MgH, {sup 25}MgH, and {sup 26}MgH molecules at elevated temperatures: Corrections due to unbound states

The total partition functions Q(T) and their first two moments Q{sup ′}(T) and Q{sup ″}(T), together with the isobaric heat capacities C{sub p}(T), are computed a priori for three major MgH isotopologues on the temperature range of T = 100–3000 K using the recent highly accurate potential energy curve, spin-rotation, and non-adiabatic correction functions of Henderson et al. [J. Phys. Chem. A 117, 13373 (2013)]. Nuclear motion computations are carried out on the ground electronic state to determine the (ro)vibrational energy levels and the scattering phase shifts. The effect of resonance states is found to be significant above about 1000 K and it increases with temperature. Even very short-lived states, due to their relatively large number, have significant contributions to Q(T) at elevated temperatures. The contribution of scattering states is around one fourth of that of resonance states but opposite in sign. Uncertainty estimates are given for the possible error sources, suggesting that all computed thermochemical properties have an accuracy better than 0.005% up to 1200 K. Between 1200 and 2500 K, the uncertainties can rise to around 0.1%, while between 2500 K and 3000 K, a further increase to 0.5% might be observed for Q{sup ″}(T) and C{sub p}(T),more » principally due to the neglect of excited electronic states. The accurate thermochemical data determined are presented in the supplementary material for the three isotopologues of {sup 24}MgH, {sup 25}MgH, and {sup 26}MgH at 1 K increments. These data, which differ significantly from older standard data, should prove useful for astronomical models incorporating thermodynamic properties of these species.« less
Authors:
 [1] ;  [1] ;  [2]
  1. MTA-ELTE Research Group on Complex Chemical Systems, P.O. Box 32, H-1518 Budapest 112 (Hungary)
  2. (Hungary)
Publication Date:
OSTI Identifier:
22415449
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 142; Journal Issue: 1; Other Information: (c) 2015 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
74 ATOMIC AND MOLECULAR PHYSICS; CALCULATION METHODS; CORRECTIONS; DIAGRAMS; ENERGY LEVELS; MAGNESIUM 24; MAGNESIUM 25; MAGNESIUM 26; MAGNESIUM HYDRIDES; MOLECULES; PARTITION FUNCTIONS; PHASE SHIFT; POTENTIAL ENERGY; ROTATION; SCATTERING; SPECIFIC HEAT; SPIN; TEMPERATURE DEPENDENCE