Relativistic corrections to the ground states of HD and D2 calculated without using the Born–Oppenheimer approximation

Literature Information

Publication Date 2018-09-06
DOI 10.1039/C8CP04586K
Impact Factor 3.676
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Abstract

The Schrödinger equation for the ground states of the hydrogen molecules HD and D2 is solved variationally by treating the constituent particles of HD or D2 on the same footing without assuming the Born–Oppenheimer approximation. The variational basis sets are constructed using Hylleraas coordinates that are traditionally adopted for few-electron atomic systems. The nonrelativistic energy eigenvalues are converged to the level of 10−6 cm−1. The leading-order relativistic corrections, including relativistic recoil terms, are calculated rigorously. Together with the higher-order relativistic and quantum electrodynamic corrections obtained by the Pachucki's group [Phys. Rev. A., 2017, 95, 052506; Phys. Rev. Lett., 2018, 120, 153001], we determine the dissociation energy of D2 to be 36748.36240(28) cm−1, which agrees with the recent experimental result of Liu et al. [J. Chem. Phys., 2010, 132, 154301] 36748.36286(68) cm−1. For HD, the dissociation energy determined by us is 36405.78252(27) cm−1, which deviates from the most accurate experimental result of Sprecher et al. [J. Chem. Phys., 2010, 133, 111102] 36405.78366(36) cm−1 by about 2σ.

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DOI: 10.1039/C6AN90044E

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
CiteScore: 5.5
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Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.

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