1Σu and 1Πu states of the hydrogen molecule: Nonadiabatic couplings and vibrational levels

Wolniewicz, L.; Orlikowski, T.; Staszewska, G.

doi:10.1016/j.jms.2006.04.020

Cited by 51 publications

(66 citation statements)

References 16 publications

(36 reference statements)

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“…The measured energies are consistent with the theoretical results of Kirrander and Jungen [13], who used the ab initio potentials of Wolniewicz et al [14,15], to perform nonadiabatic coupling calculations of the ion-pair levels of H 2 above the (1s; 3l) dissociation limit. We find that a consecutive numbering from the lower vibrational levels of the B 00 B 1 R þ u state can be continued through the avoided crossing of the diabatic ion-pair potential with the ð1s; 3lÞ dissociation asymptote without interruption to include the ion-pair levels observed above it.…”

Section: Introductionsupporting

confidence: 85%

“…Fig. 2 includes corresponding quantum defects for the v 0 ¼ 0-16 levels as well as those for the theoretical term energies of the v 0 ¼ 43, 45, 47-49, 54 and 55 vibrational levels [15], which were not observed by Chartrand et al [11]. The quantum defect plot shown in Fig.…”

Section: Heavy Rydberg Analysismentioning

confidence: 85%

“…We first consider HR behaviour in the B 00 B 1 R þ u state below the ð1s; 3lÞ threshold and extend the previous quantum defect analysis by Lawley and Donovan [12] to include the lower, below-barrier, outer-well vibrational levels, v 0 ¼ 0-16, predicted by Wolniewicz et al [15] Note that v 0 corresponds to outer-well vibrational numbering exclusive of the inner-well vibrational levels. These theoretical predictions agree with experiment, where available [19,20], to within $ 0:1 cm À1 .…”

Section: Heavy Rydberg Analysismentioning

confidence: 99%

See 2 more Smart Citations

Continuity of heavy Rydberg behaviour in the ungerade ion-pair states of H 2

Chartrand

Donovan

Lawley

et al. 2017

Chemical Physics Letters

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Section: Introductionsupporting

confidence: 85%

Section: Heavy Rydberg Analysismentioning

confidence: 85%

Section: Heavy Rydberg Analysismentioning

confidence: 99%

See 1 more Smart Citation

Continuity of heavy Rydberg behaviour in the ungerade ion-pair states of H 2

Chartrand

Donovan

Lawley

et al. 2017

Chemical Physics Letters

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“…For reasons of consistency we have not used the recent non-adiabatic coupling functions published by Wolniewicz et al 49 At the time when the emission bands were analyzed, 14 no ab initio coupling functions between D and other 1 − u states were available. Therefore, the D state was treated in the adiabatic approximation.…”

Section: A Coupled Equations Calculationsmentioning

confidence: 99%

Theory of vibronic interactions in D2 and H2: A comparison between multichannel-quantum-defect and coupled-equation approaches

Glass‐Maujean

Jungen

Roudjane

et al. 2011

The Journal of Chemical Physics

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New experimental energy levels for the 2pπC(1)Π(u)(-) state of D(2) are reported extending up to the dissociation limit and including rotational quantum numbers up to N = 10. These data are extracted from recent high resolution optical emission spectra, and they are used for a detailed comparison of two theoretical approaches, both of which are fully ab initio and are based on the same state-of-the-art clamped-nuclei potential energy curves. These are the coupled differential equations (CE) and the multichannel quantum defect theory (MQDT) approaches, each of which accounts for adiabatic corrections and non-adiabatic couplings. Both theoretical approaches reproduce the experimental levels to within a fraction of a wavenumber unit (cm(-1)) for the lower vibrational quantum numbers, with the MQDT surpassing the CE method. As the dissociation limit is approached, the residuals observed-calculated increase up to several cm(-1) and the MQDT method is up to a factor of two less accurate than the CE method. The same analysis is carried out with existing data for the H(2) isotopomer and yields similar results. An analogous comparison is also made for the 3pπD(1)Π(u)(-) and 4pπD('1)Π(u)(-) states for both isotopomers, where the MQDT is found to be superior to the CE approach.

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“…New ab initio data on coupling operators have been published very recently by Wolniewicz et al 20 As our analysis was already completed using the former ab initio data ͑Ref. 4͒, they may slightly change the percentages of electronic characters without changing the main features discussed above.…”

Section: Level Perturbationsmentioning

confidence: 99%

High resolution vacuum ultraviolet emission spectrum of D2: The B′Σu+1→XΣg+1 band system

Roudjane

Tchang-Brillet

Launay

2007

The Journal of Chemical Physics

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In this work, we have extended our previous high resolution study of the vacuum ultraviolet emission spectrum of the D2 molecule [M. Roudjane, et al. J. Chem. Phys. 125, 214305 (2006)] up to 124.2 nm in order to investigate the B' 1Sigmau+-->X 1Sigmag+ band system. The analysis of the spectrum has been carried out by means of a complex spectrum visual identification code IDEN [V. I. Azarov, Phys. Scr. 44, 528 (1991); 48, 656, (1993)] and supported by theoretical calculations using ab initio data [L. Wolniewicz, J. Chem. Phys. 103, 1792 (1995); 99, 1851 (1993); G. Staszewska and L. Wolniewicz, J. Mol. Spectrosc. 212, 208 (2002); L. Wolniewicz and G. Staszewska, 220, 45 (2003)] which provided level energies and transition probabilities. More than 1480 new emission lines have been observed and 109 bands belonging to the B' 1Sigmau+-->X 1Sigmag+ system have been identified between 84.1 and 121.6 nm. Except for the upsilon'-0 bands that were reported in absorption [I. Dabrowski and G. Herzberg, Can. J. Phys. 52, 1110 (1974)], all the upsilon'-upsilon" bands are reported here for the first time. The analysis led to the determination of 111 rovibronic energy levels in the B' 1Sigmau+ state, of which 31 with higher rotational numbers J are new. Observed perturbations are accounted for through a set of coupled equations involving the four excited electronic states B 1Sigmau+, B' 1Sigmau+, C 1Piu, and D 1Piu and including nonadiabatic couplings. The solution of this set provides the percent contribution of these four states to each of the observed rovibronic level.

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1Σu and 1Πu states of the hydrogen molecule: Nonadiabatic couplings and vibrational levels

Cited by 51 publications

References 16 publications

Continuity of heavy Rydberg behaviour in the ungerade ion-pair states of H 2

Continuity of heavy Rydberg behaviour in the ungerade ion-pair states of H 2

Theory of vibronic interactions in D2 and H2: A comparison between multichannel-quantum-defect and coupled-equation approaches

High resolution vacuum ultraviolet emission spectrum of D2: The B′Σu+1→XΣg+1 band system

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