Theoretical ab initio study of the electronic states of KrH and KrH+: Quantum defect and complex coordinate calculations on the Rydberg states of KrH

Abstract

Potential energy curves have been calculated for the ground and excited electronic states of KrH and the cation KrH ϩ by ab initio configuration interaction calculations using effective core potentials for Kr. Quantum defect functions have been determined from the ab initio potentials of the low-lying Rydberg states of KrH and potential energy curves have been generated for higher n (s,p,d) Rydberg states. The resulting bound-bound transition energies are in excellent agreement with experimental data. The interaction of the 5p B 2 ⌸ state with the 5s and 5p A 2 ⌺ and C 2 ⌺ ϩ states and their predissociation by X 2 ⌺ ϩ has been treated by multistate complex scaling calculations for both KrH and KrD. Much larger predissociation widths are obtained in KrH than in KrD, in agreement with experimental observations.

Ab initio and quantum-defect calculations for the Rydberg states of ArH

“…1 and 2 for the lowest 2 S 1 , 2 P and 2 D states, is similar to those for NeH 48 and KrH. 49 The dashed curves give the MQDT predictions for higher members of the various series. At small separation the excited ArH states take the form of Rydberg series converging to the ground X 1 S 1 state of the ArH 1 cation, while at intermediate and large internuclear distances they cross the Rydberg series converging to the lowest excited states of the cation.…”

Ab initio potential energy curves and transition dipole moments for the low-lying electronic states of NeH+

“…The second asymptote, Ne + ( 2 P 3/2,1/2 ) + H ( 2 S 1/2 ), lies 64251 cm -1 above the first one [34] and results in 1 Σ + , 1 Π, 3 Σ + and 3 Π molecular states. These excited electronic states are unknown experimentally, and to be consistent with state labeling of ArH + , KrH + and XeH + ions [35][36][37], we labeled them as A 1 Σ + , B 1 Π, a 3 Σ + and b 3 Π, respectively. The third asymptote, i.e., Ne (2p 5 3s 1 ) + H + , lies about 134200 cm -1 above the ground state [34], and we did not include it in our calculations.…”

Ionization of Hydrogen Rydberg Molecules at a Metal Surface

“…It should be noted that the extension of basis set multiplies the required number of functions by an order of magnitude. In addition, a full treatment would also require inclusion of predissociation [which could also be tackled using a complex scaling approach [20] ], and also determination of the evolution of the Rydberg wave function as it passes a multitude of avoided crossings in the Stark map as the field is ramped up prior to surface interaction. It is hoped that the present work will stimulate detailed theoretical investigations of this type.…”