Convergent energies and anharmonic vibrational spectra of Ca2H2 and Ca2H4 constitutional isomers

Bowman, Michael C.; Douberly, Gary E.; Schaefer, Henry F.

doi:10.1039/c9cp01643k

Convergent energies and anharmonic vibrational spectra of Ca2H2 and Ca2H4 constitutional isomers

Journal Article · Wed May 01 00:00:00 EDT 2019 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/c9cp01643k· OSTI ID:1612990

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Univ. of Georgia, Athens, GA (United States)

Three constitutional isomers of both Ca₂H₂ and Ca₂H₄ have been characterized with molecular electronic structure theory. Correlation methods as complete as CCSDT(Q) and basis sets as large as cc-pwCV5Z have been used to converge the relative energies within chemical accuracy (≤1 kcal mol^-1). Anharmonic vibrational frequencies were computed using second-order vibrational perturbation theory employing CCSD(T)/cc-pwCVTZ cubic and quartic force-fields and a CCSD(T)/cc-pwCVQZ quadratic force field. The monobridged [Ca(μ₂-H)CaH] and dibridged [Ca(μ₂-H)₂Ca] isomers of Ca₂H₂ were predicted to lie 6.5 and 12.9 kcal mol^-1 below the energy of the classical HCaCaH linear isomer, respectively. Despite the energetic favorability of the bridged Ca₂H₂ isomers, we conclude (surprisingly) that only the higher energy linear structure has been observed in the laboratory. At 0 K, the tribridged [Ca(μ₂-H)₃CaH] isomer of Ca₂H₄ is predicted to be enthalpically favored by 0.9 kcal mol^-1 in comparison to the enthalpy of the dibridged [HCa(μ₂-H)₂CaH] structure. Comparison of experiment with our computed frequencies suggests that the observed vibrational features arise from both the dibridged and the tribridged Ca₂H₄ structures.

View Accepted Manuscript (DOE)

Research Organization:: University of Georgia, Athens, GA (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0018412

OSTI ID:: 1612990

Alternate ID(s):: OSTI ID: 1512536

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 21 Vol. 21; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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