TY - JOUR

T1 - Accurate, two-state ab initio study of the ground and first-excited states of He2 +, including exact treatment of all Born-Oppenheimer correction terms

AU - Xie, Junkai

AU - Poirier, Bill

AU - Gellene, Gregory I.

N1 - Funding Information:
Grateful acknowledgment is made to the Robert A. Welch Foundation (Grant Nos. D-1293 and D-1523) for support of this work. Acknowledgment is also made to the Office of Advanced Scientific Computing Research, Mathematical, Information, and Computational Sciences Division of the U.S. Department of Energy under Contract No. DE-FG03-02ER25534.

PY - 2005/5/8

Y1 - 2005/5/8

N2 - Born-Oppenheimer (BO) potentials for the ground and first-excited electronic states of He2+ are determined using high level ab initio techniques for internuclear separations R of 1.2-100 bohrs and accurately fit to analytical functions. In the present formulation, the BO potentials are nuclear mass independent, and the corresponding BO approximation is obtained by ignoring four terms of the full rovibronic Hamiltonian. These four Born-Oppenheimer correction (BOC) terms are as follows: (1) mass polarization, (2) electronic orbital angular momentum, (3) first derivative with respect to R, and (4) second derivative with respect to R. In order to enable an exact rovibronic calculation, each of the four BOC terms are computed as a function of R, for the two electronic states and for their coupling, without any approximation or use of empirical parameters. Each of the BOC terms is found to make a contribution to the total energy over at least some portion of the range of R investigated. Interestingly, the most significant coupling contribution arises from the electronic orbital angular momentum term, which is evidently computed for the first time in this work. Although several BOC curves exhibit a nontrivial dependence on R, all are accurately fit to analytical functions. The resulting functions, together with the BO potentials, are used to compute exact rovibronic energy levels for He3 He+3, He3 He+4, and He4 He+4. Comparison to available high quality experimental data indicates that the present BOC potentials provide the most accurate representation currently available of both the low- and high-lying levels of the ground electronic state and the bound levels of the excited state.

AB - Born-Oppenheimer (BO) potentials for the ground and first-excited electronic states of He2+ are determined using high level ab initio techniques for internuclear separations R of 1.2-100 bohrs and accurately fit to analytical functions. In the present formulation, the BO potentials are nuclear mass independent, and the corresponding BO approximation is obtained by ignoring four terms of the full rovibronic Hamiltonian. These four Born-Oppenheimer correction (BOC) terms are as follows: (1) mass polarization, (2) electronic orbital angular momentum, (3) first derivative with respect to R, and (4) second derivative with respect to R. In order to enable an exact rovibronic calculation, each of the four BOC terms are computed as a function of R, for the two electronic states and for their coupling, without any approximation or use of empirical parameters. Each of the BOC terms is found to make a contribution to the total energy over at least some portion of the range of R investigated. Interestingly, the most significant coupling contribution arises from the electronic orbital angular momentum term, which is evidently computed for the first time in this work. Although several BOC curves exhibit a nontrivial dependence on R, all are accurately fit to analytical functions. The resulting functions, together with the BO potentials, are used to compute exact rovibronic energy levels for He3 He+3, He3 He+4, and He4 He+4. Comparison to available high quality experimental data indicates that the present BOC potentials provide the most accurate representation currently available of both the low- and high-lying levels of the ground electronic state and the bound levels of the excited state.

UR - http://www.scopus.com/inward/record.url?scp=34548106889&partnerID=8YFLogxK

U2 - 10.1063/1.1891685

DO - 10.1063/1.1891685

M3 - Article

C2 - 15918707

AN - SCOPUS:34548106889

VL - 122

JO - The Journal of Chemical Physics

JF - The Journal of Chemical Physics

SN - 0021-9606

IS - 18

M1 - 184310

ER -