Incorporation of electronically nonadiabatic effects into bimolecular reactive systems. II. The collinear (H2 + H+, H2+ + H) system

Top, Z.H.; Baer, Michael

doi:10.1016/0301-0104(77)87060-2

Cited by 105 publications

(29 citation statements)

References 38 publications

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“…Since all contours are assumed to be in the plane no contour is capable to surround this axis (which is in the plane) and therefore a different way to include the RT effect has to be found. Based on our past experience [19][20][21] a trustful way to include the RT effect is to let the contours intersect the degeneracy line and in this way to enable the corresponding NACT matrix elements to pick up the resulting RT effect. The only problem encountered here is that these calculated NACTs are extremely spiky-reminiscent of the Dirac δ-function (see, e.g., Fig.…”

Section: (B))mentioning

confidence: 99%

“…It is well known that at each such intersection point, along a short interval perpendicular to the collinear axis, is formed a spiky non-zero NACT (in this case an angular NACT) with features reminiscent of a Dirac δ-function. 21(b), 31 Thus, our first tendency is to assume that the angular RT-NACTs in the planar CS take the form 3…”

Section: Presentation Of the Intra-planar Rt Nactmentioning

confidence: 99%

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A tri-atomic Renner-Teller system entangled with Jahn-Teller conical intersections

Csehi

Bende

Halász

et al. 2013

The Journal of Chemical Physics

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The present study concentrates on a situation where a Renner-Teller (RT) system is entangled with Jahn-Teller (JT) conical intersections. Studies of this type were performed in the past for contours that surround the RT seam located along the collinear axis [see, for instance, G. J. Halász, Á. Vibók, R. Baer, and M. Baer, J. Chem. Phys. 125, 094102 (2006)]. The present study is characterized by planar contours that intersect the collinear axis, thus, forming a unique type of RT-non-adiabatic coupling terms (NACT) expressed in terms of Dirac-δ functions. Consequently, to calculate the required adiabatic-to-diabatic (mixing) angles, a new approach is developed. During this study we revealed the existence of a novel molecular parameter, η, which yields the coupling between the RT and the JT NACTs. This parameter was found to be a pure number η = 2 √ 2/π (and therefore independent of any particular molecular system) and is designated as Renner-Jahn coupling parameter. The present study also reveals an unexpected result of the following kind: It is well known that each (complete) group of states, responsible for either the JT-effect or the RT-effect, forms a Hilbert space of its own. However, the entanglement between these two effects forms a third effect, namely, the RT/JT effect and the states that take part in it form a different Hilbert space.

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Section: (B))mentioning

confidence: 99%

Section: Presentation Of the Intra-planar Rt Nactmentioning

confidence: 99%

A tri-atomic Renner-Teller system entangled with Jahn-Teller conical intersections

Csehi

Bende

Halász

et al. 2013

The Journal of Chemical Physics

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“…The traditional solution consists of finding an electronic basis set that converts the NACMEs into nonsingular operators or eventually fully removes them. Such a basis set is called diabatic [3][4][5][6][7][8][9][10][11][12][13][14][15][16][17][18][19] by comparison with the former adiabatic one. Two types of diabatic bases are apparently possible: the diabatic I basis that removes only the singular part of the NACMEs, and the strictly diabatic [10,11,13,15,17] (diabatic II) basis that fully removes the NACMEs decoupling the nuclear equations of motion.…”

mentioning

confidence: 99%

“…Despite the wide use of diabatic basis sets, the existence of an orthogonal transformation leading to a strictly diabatic basis has been a problematic issue since the seminal works by McLachlan [3,20], Mead and Truhlar [10] (see also Refs. [11,13,15,17]), and Baer [7][8][9] (for a recent debate, see Refs. [21,22]).…”

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confidence: 99%

Existence of strictly diabatic basis sets for the two‐state problem

Kryachko

Varandas

2002

Int J of Quantum Chemistry

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Some new properties of the nonadiabatic coupling elements are derived, in particular the orthogonality and gauge invariance of their longitudinal and transverse components. A method for constructing a strictly diabatic basis set that makes both the transverse and longitudinal components of the nonadiabatic coupling elements of the two-state problem vanish identically and is based on introducing overlap between the electronic states in the vicinity of the crossing seam is proposed.

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“…Baer extended this procedure to the atom-diatom collision [24] and applied it successfully in various cases [5,6]_ According to this procedure, the transformation matrix (called below G) is obtained as a solution of a firstorder vector differential equation: V*G+T(')G=O, where V is the vectorial covariant gradient operator in terms ofN nuclear coordinates and T(l) is a vector matrix the elements of which are antisymmetric.…”

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confidence: 99%

Adiabatic-to-diabatic electronic state transformation and curvilinear nuclear coordinates for molecular systems

Chapuisat¹,

Nauts²,

Dehareng-Dao³

1983

Chemical Physics Letters

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Incorporation of electronically nonadiabatic effects into bimolecular reactive systems. II. The collinear (H2 + H+, H2+ + H) system

Cited by 105 publications

References 38 publications

A tri-atomic Renner-Teller system entangled with Jahn-Teller conical intersections

A tri-atomic Renner-Teller system entangled with Jahn-Teller conical intersections

Existence of strictly diabatic basis sets for the two‐state problem

Adiabatic-to-diabatic electronic state transformation and curvilinear nuclear coordinates for molecular systems

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