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/Subject (In this Communication we present the first theoretical/numerical treatment of nonadiabatic coupling terms \(NACT\) that originate from the Renner-Teller \(RT\) model, namely, those that follow from the splitting of an electronic level of a linear molecule when it becomes bent. These two newly formed states are characterized by different symmetries and are designated as AA and BB. Our main findings: \(1\) TheRT NACTs are quantized as long as they are calculated close enough to collinear configuration of the molecule \(in this case HNHHNH\). Their value is \\tau=1\\tau=1 \(the Jahn-Teller values in similar situations, are \\tau=1/2 \\tau=1/2\). \(2\) Calculation of RT NACTs at bent configurations \(i.e., at a distance from the linear axis\) yield decreased values, sometimes by more than 50 percent. This last finding implies that in strongly bent configurations the two-state Hilbert subspace \(formed by the above mentioned AA and BB states\) is affected by upper states, most likely via Jahn-Teller conical intersections. \(3\) This study has also important practical implications. The fact that the RT NACTs decrease in \(strongly\) bent situations implies that analyzing spectroscopic data employing only the two pi-pi-states may not be sufficient in order to achieve the required accuracy.)
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2006
D matrix analysis of the Renner-Teller effect: An accurate three-state diabatization for NH 2
Gabor J. Hal{\'a}sz
{\'A}gnes Vib{\'o}k
Roi Baer
Michael Baer
In this Communication we present the first theoretical/numerical treatment of nonadiabatic coupling terms (NACT) that originate from the Renner-Teller (RT) model, namely, those that follow from the splitting of an electronic level of a linear molecule when it becomes bent. These two newly formed states are characterized by different symmetries and are designated as AA and BB. Our main findings: (1) TheRT NACTs are quantized as long as they are calculated close enough to collinear configuration of the molecule (in this case HNHHNH). Their value is \tau=1\tau=1 (the Jahn-Teller values in similar situations, are \tau=1/2 \tau=1/2). (2) Calculation of RT NACTs at bent configurations (i.e., at a distance from the linear axis) yield decreased values, sometimes by more than 50 percent. This last finding implies that in strongly bent configurations the two-state Hilbert subspace (formed by the above mentioned AA and BB states) is affected by upper states, most likely via Jahn-Teller conical intersections. (3) This study has also important practical implications. The fact that the RT NACTs decrease in (strongly) bent situations implies that analyzing spectroscopic data employing only the two pi-pi-states may not be sufficient in order to achieve the required accuracy.
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{\'A}gnes Vib{\'o}k
Roi Baer
Michael Baer
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