Separability of H2O molecular potential surfaces in hyperspherical coordinates via adiabatic approximation

Daněk, Jiří; Lin, C. D.

doi:10.1103/physreva.102.042809

Separability of $H_{2} O$ molecular potential surfaces in hyperspherical coordinates via adiabatic approximation

Journal Article · Mon Oct 12 04:00:00 EDT 2020 · Physical Review A

DOI:https://doi.org/10.1103/physreva.102.042809· OSTI ID:1849916

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Kansas State Univ., Manhattan, KS (United States); OSTI
Kansas State Univ., Manhattan, KS (United States)

An adiabatic scheme for separation of the three-dimensional (3D) nuclear dynamics on the ground electronic Born-Oppenheimer potential energy surface of an H₂O molecule in hyperspherical coordinates is presented. It is found that the three vibrational modes are weakly coupled and the 3D vibrational wave function can be approximated as a product of three separable functions: one represented by the hyperradius and two by the two hyperangles individually. Additionally, this framework is then used for investigation of the formation and the role of a saddlelike barrier arising in the two hyperspherical angles that is to moderate the OH + H dissociation process. In order to test the validity of the framework, vibrational states with energies up to 19 500 cm^-1 are constructed under the assumptions of adiabaticity and separability and compared to full three-dimensional high-precision numerical calculations yielding remarkable correspondence. As a result we present a simple construction scheme for separated molecular vibration states as the first step towards theoretical investigation of laser-driven molecular dynamics of triatomic molecules.

View Accepted Manuscript (DOE)

Research Organization:: Kansas State Univ., Manhattan, KS (United States)

Sponsoring Organization:: USDOE Office of Science (SC), Basic Energy Sciences (BES). Chemical Sciences, Geosciences & Biosciences Division

Grant/Contract Number:: FG02-86ER13491

OSTI ID:: 1849916

Journal Information:: Physical Review A, Journal Name: Physical Review A Journal Issue: 4 Vol. 102; ISSN PLRAAN; ISSN 2469-9926

Publisher:: American Physical Society (APS)Copyright Statement

Country of Publication:: United States

Language:: English

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74 ATOMIC AND MOLECULAR PHYSICS
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Separability of H2O molecular potential surfaces in hyperspherical coordinates via adiabatic approximation

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Separability of $H_{2} O$ molecular potential surfaces in hyperspherical coordinates via adiabatic approximation