Abstract
An algorithm is proposed, based principally on an earlier proposition of Flaud and co-workers [Mol. Phys. 32 (1976) 499], that inverts the information contained in uniquely assigned experimental rotational-vibrational transitions in order to obtain measured active rotational-vibrational energy levels (MARVEL). The procedure starts with collecting, critically evaluating, selecting, and compiling all available measured transitions, including assignments and uncertainties, into a single database. Then, spectroscopic networks (SN) are determined which contain all interconnecting rotational-vibrational energy levels supported by the grand database of the selected transitions. Adjustment of the uncertainties of the lines is performed next, with the help of a robust weighting strategy, until a self-consistent set of lines and uncertainties is achieved. Inversion of the transitions through a weighted least-squares-type procedure results in MARVEL energy levels and associated uncertainties. Local sensitivity coefficients could be computed for each energy level. The resulting set of MARVEL levels is called active as when new experimental measurements become available the same evaluation, adjustment, and inversion procedure should be repeated in order to obtain more dependable energy levels and uncertainties. MARVEL is tested on the example of the H2 17O isotopologue of water and a list of 2736 dependable energy levels, based on 8369 transitions, has been obtained.
| Original language | English |
|---|---|
| Pages (from-to) | 115-125 |
| Number of pages | 11 |
| Journal | Journal of Molecular Spectroscopy |
| Volume | 245 |
| Issue number | 2 |
| DOIs | |
| Publication status | Published - Oct 2007 |
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Keywords
- H O
- MARVEL
- Robust fitting
- Rotational-vibrational energy levels
- Uncertainties
ASJC Scopus subject areas
- Physical and Theoretical Chemistry
- Spectroscopy
- Atomic and Molecular Physics, and Optics
Cite this
MARVEL : measured active rotational-vibrational energy levels. / Furtenbacher, T.; Császár, A.; Tennyson, Jonathan.
In: Journal of Molecular Spectroscopy, Vol. 245, No. 2, 10.2007, p. 115-125.Research output: Contribution to journal › Article
}
TY - JOUR
T1 - MARVEL
T2 - measured active rotational-vibrational energy levels
AU - Furtenbacher, T.
AU - Császár, A.
AU - Tennyson, Jonathan
PY - 2007/10
Y1 - 2007/10
N2 - An algorithm is proposed, based principally on an earlier proposition of Flaud and co-workers [Mol. Phys. 32 (1976) 499], that inverts the information contained in uniquely assigned experimental rotational-vibrational transitions in order to obtain measured active rotational-vibrational energy levels (MARVEL). The procedure starts with collecting, critically evaluating, selecting, and compiling all available measured transitions, including assignments and uncertainties, into a single database. Then, spectroscopic networks (SN) are determined which contain all interconnecting rotational-vibrational energy levels supported by the grand database of the selected transitions. Adjustment of the uncertainties of the lines is performed next, with the help of a robust weighting strategy, until a self-consistent set of lines and uncertainties is achieved. Inversion of the transitions through a weighted least-squares-type procedure results in MARVEL energy levels and associated uncertainties. Local sensitivity coefficients could be computed for each energy level. The resulting set of MARVEL levels is called active as when new experimental measurements become available the same evaluation, adjustment, and inversion procedure should be repeated in order to obtain more dependable energy levels and uncertainties. MARVEL is tested on the example of the H2 17O isotopologue of water and a list of 2736 dependable energy levels, based on 8369 transitions, has been obtained.
AB - An algorithm is proposed, based principally on an earlier proposition of Flaud and co-workers [Mol. Phys. 32 (1976) 499], that inverts the information contained in uniquely assigned experimental rotational-vibrational transitions in order to obtain measured active rotational-vibrational energy levels (MARVEL). The procedure starts with collecting, critically evaluating, selecting, and compiling all available measured transitions, including assignments and uncertainties, into a single database. Then, spectroscopic networks (SN) are determined which contain all interconnecting rotational-vibrational energy levels supported by the grand database of the selected transitions. Adjustment of the uncertainties of the lines is performed next, with the help of a robust weighting strategy, until a self-consistent set of lines and uncertainties is achieved. Inversion of the transitions through a weighted least-squares-type procedure results in MARVEL energy levels and associated uncertainties. Local sensitivity coefficients could be computed for each energy level. The resulting set of MARVEL levels is called active as when new experimental measurements become available the same evaluation, adjustment, and inversion procedure should be repeated in order to obtain more dependable energy levels and uncertainties. MARVEL is tested on the example of the H2 17O isotopologue of water and a list of 2736 dependable energy levels, based on 8369 transitions, has been obtained.
KW - H O
KW - MARVEL
KW - Robust fitting
KW - Rotational-vibrational energy levels
KW - Uncertainties
UR - http://www.scopus.com/inward/record.url?scp=34848865640&partnerID=8YFLogxK
UR - http://www.scopus.com/inward/citedby.url?scp=34848865640&partnerID=8YFLogxK
U2 - 10.1016/j.jms.2007.07.005
DO - 10.1016/j.jms.2007.07.005
M3 - Article
VL - 245
SP - 115
EP - 125
JO - Journal of Molecular Spectroscopy
JF - Journal of Molecular Spectroscopy
SN - 0022-2852
IS - 2
ER -