Photoionization-induced dynamics of the ammonia cation studied by wave packet calculations using curvilinear coordinates

Viel, Alexandra; Eisfeld, Wolfgang; Evenhuis, Christian; Manthe, Uwe

doi:10.1016/j.chemphys.2007.10.001

Cited by 29 publications

(37 citation statements)

References 33 publications

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“…The experimental bandwidth is also well reproduced by FC calculations; Rabelais' experimental spectrum shows sixteen wellresolved peaks, with a little not resolved tail, whereas the theoretical one exhibits one more. The computed spectrum also shows the presence of a second much weaker progression, which the calculation assigns to transitions to vibrational states with excitations on the bending mode m 2 and a single quantum on the totally symmetric stretching mode m 1 , in agreement with previous theoretical results [10,13,14]. The weaker progression is very well resolved in the high-resolution spectrum of Edvardsson et al [38] who tentatively assigned it to transitions to a vibrational progression of the asymmetric bending mode with one more quantum on the symmetric bending mode m 2 .…”

Section: Theoretical Approachsupporting

confidence: 88%

“…The most successful attempts to rationalize the photoelectron spectrum of ammonia through the computation of Franck-Condon factors was based on procedures that overcome Duschinsky's transformation, avoiding the use of normal modes of both electronic states [11][12][13][14]. Recently, a very satisfying reproduction of the photoelectron spectrum of ammonia, based on Duschinsky's transformation and the Cartesian representation of the normal coordinates, has been obtained by using a two-dimensional approach, including the symmetric stretching and bending coordinates.…”

Section: Introductionmentioning

confidence: 99%

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Franck–Condon factors in curvilinear coordinates: the photoelectron spectrum of ammonia

et al. 2012

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An approach to the calculation of FranckCondon factors in curvilinear coordinates is outlined. The approach is based on curvilinear normal coordinates, which allows for an easy extension of Duschinsky's transformation to the case of curvilinear coordinates, and on the power series expansion of the kinetic energy operator. Its usefulness in the case of molecules undergoing large displacements of their equilibrium nuclear configurations upon excitation is then demonstrated by an application to the vibrational structure of the photoelectron spectrum of ammonia, using an anharmonic potential only for the symmetric stretching and bending coordinates of the radical cation.

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Section: Theoretical Approachsupporting

confidence: 88%

Section: Introductionmentioning

confidence: 99%

Franck–Condon factors in curvilinear coordinates: the photoelectron spectrum of ammonia

et al. 2012

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“…[49][50][51] However, curvilinear coordinates lead to complicated expressions of the kinetic energy operator. Polyspherical coordinates as described in Refs.…”

Section: Conceptual Developmentsmentioning

confidence: 99%

A generalised vibronic-coupling Hamiltonian model for benzopyran

Joubert-Doriol

Lasorne

Lauvergnat

et al. 2014

The Journal of Chemical Physics

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A new general model for describing intersecting multidimensional potential energy surfaces when motions of large amplitude are involved is presented. This model can be seen as an extension of the vibronic coupling models of Köppel et al. ["Multimode molecular dynamics beyond the Born-Oppenheimer approximation," Adv. Chem. Phys. 57, 59 (1984)]. In contrast to the original vibronic coupling models, here the number of diabatic states is larger than the number of adiabatic states and curvilinear coordinates are used in a systematic way. Following general considerations, the approach is applied to the fitting of the potential energy surfaces for the very complex nonadiabatic photodynamics of benzopyran. Preliminary results are presented at the complete active space self-consistent field level of theory and with up to 12 active degrees of freedom. Special emphasis is placed on the physical interpretation of the diabatic states and on the influence of the various degrees of freedom on the fit.

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“…So far we have used point group symmetry (which in our case is isomorphic to CNPI symmetry) and expanded the diabatic Hamiltonian in properly symmetrized coordinates and polynomials for typical Jahn-Teller systems. [50][51][52][53] This strategy was also followed by some other groups. [54][55][56][57] The present work is an extension of our method to allow for a highly accurate representation of Jahn-Teller systems including the proper direct dissociation asymptotes.…”

Section: Introductionmentioning

confidence: 99%

Full-dimensional diabatic potential energy surfaces including dissociation: The 2E″ state of NO3

Eisfeld

Vieuxmaire

Viel

2014

The Journal of Chemical Physics

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A scheme to produce accurate full-dimensional coupled diabatic potential energy surfaces including dissociative regions and suitable for dynamical calculations is proposed. The scheme is successfully applied to model the two-sheeted surface of the (2)E″ state of the NO3 radical. An accurate potential energy surface for the NO₃⁻ anion ground state is developed as well. Both surfaces are based on high-level ab initio calculations. The model consists of a diabatic potential matrix, which is expanded to higher order in terms of symmetry polynomials of symmetry coordinates. The choice of coordinates is key for the accuracy of the obtained potential energy surfaces and is discussed in detail. A second central aspect is the generation of reference data to fit the expansion coefficients of the model for which a stochastic approach is proposed. A third ingredient is a new and simple scheme to handle problematic regions of the potential energy surfaces, resulting from the massive undersampling by the reference data unavoidable for high-dimensional problems. The final analytical diabatic surfaces are used to compute the lowest vibrational levels of NO₃⁻ and the photo-electron detachment spectrum of NO₃⁻ leading to the neutral radical in the (2)E″ state by full dimensional multi-surface wave-packet propagation for NO3 performed using the Multi-Configuration Time Dependent Hartree method. The achieved agreement of the simulations with available experimental data demonstrates the power of the proposed scheme and the high quality of the obtained potential energy surfaces.

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Photoionization-induced dynamics of the ammonia cation studied by wave packet calculations using curvilinear coordinates

Cited by 29 publications

References 33 publications

Franck–Condon factors in curvilinear coordinates: the photoelectron spectrum of ammonia

Franck–Condon factors in curvilinear coordinates: the photoelectron spectrum of ammonia

A generalised vibronic-coupling Hamiltonian model for benzopyran

Full-dimensional diabatic potential energy surfaces including dissociation: The 2E″ state of NO3

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