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Title: Conical intersections and diabatic potential energy surfaces for the three lowest electronic singlet states of H{sub 3}{sup +}

We calculate the adiabatic Potential Energy Surfaces (PESs) and the Non-Adiabatic Coupling Terms (NACTs) for the three lowest singlet states of H{sub 3}{sup +} in hyperspherical coordinates as functions of hyperangles (θ and ϕ) for a grid of fixed values of hyperradius (1.5 ⩽ ρ ⩽ 20 bohrs) using the MRCI level of methodology employing ab initio quantum chemistry package (MOLPRO). The NACT between the ground and the first excited state translates along the seams on the θ − ϕ space, i.e., there are six Conical Intersections (CIs) at each θ (60° ⩽ θ ⩽ 90°) within the domain, 0 ⩽ ϕ ⩽ 2π. While transforming the adiabatic PESs to the diabatic ones, such surfaces show up six crossings along those seams. Our beyond Born-Oppenheimer approach could incorporate the effect of NACTs accurately and construct single-valued, continuous, smooth, and symmetric diabatic PESs. Since the location of CIs and the spatial amplitudes of NACTs are most prominent around ρ = 10 bohrs, generally only those results are depicted.
Authors:
;  [1] ;  [2]
  1. Department of Physical Chemistry and Raman Center for Atom, Molecule and Optical Sciences, Indian Association for the Cultivation of Science, Jadavpur, Kolkata - 700 032 (India)
  2. Department of Chemistry, University of Calcutta, Kolkata - 700 009 (India)
Publication Date:
OSTI Identifier:
22423760
Resource Type:
Journal Article
Resource Relation:
Journal Name: Journal of Chemical Physics; Journal Volume: 141; Journal Issue: 20; Other Information: (c) 2014 AIP Publishing LLC; Country of input: International Atomic Energy Agency (IAEA)
Country of Publication:
United States
Language:
English
Subject:
71 CLASSICAL AND QUANTUM MECHANICS, GENERAL PHYSICS; 37 INORGANIC, ORGANIC, PHYSICAL AND ANALYTICAL CHEMISTRY; AMPLITUDES; BORN-OPPENHEIMER APPROXIMATION; COORDINATES; COUPLING; EXCITED STATES; HYDROGEN IONS 3 PLUS; SURFACES