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

Journal Article · Fri Nov 28 04:00:00 EST 2014 · Journal of Chemical Physics

DOI:https://doi.org/10.1063/1.4901986· OSTI ID:22423760

Mukherjee, Saikat; Adhikari, Satrajit ^[1]; Mukhopadhyay, Debasis ^[2]

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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)

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.

• OSTI ID: 22423760
• Journal Information: Journal of Chemical Physics, Journal Name: Journal of Chemical Physics Journal Issue: 20 Vol. 141; ISSN JCPSA6; ISSN 0021-9606
• Country of Publication: United States
• Language: English

Related Subjects

37 INORGANIC, ORGANIC, PHYSICAL, AND ANALYTICAL CHEMISTRY
71 CLASSICAL AND QUANTUM MECHANICS
GENERAL PHYSICS
AMPLITUDES
BORN-OPPENHEIMER APPROXIMATION
COORDINATES
COUPLING
EXCITED STATES
HYDROGEN IONS 3 PLUS
SURFACES