Ab initio calculations of the electronic states of AsH2 including dissociation characteristics

Alekseyev, Aleksey B.; Buenker, Robert J.; Liebermann, Heinz–Peter

doi:doi:10.1063/1.3671374

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Multiphoton dissociative ionization of tert-pentyl bromide near 265 nm

We report on the photodissociation dynamics of tert-pentyl bromide near 265 nm investigated by time-sliced velocity map imaging. The speed and angular distributions have been analyzed for both the ground-state Br(2P3/2) atom (denoted Br) and the spin–orbit excited-state Br(2P1/2) atom (denoted Br*). The speed distributions of Br and Br* atoms are all found to consist of three Gaussian components, which correlate to three independent dissociation pathways on the excited potential energy surfaces:...

Rotational and vibrational energy transfer in vibrationally excited acetylene at energies near 6560 cm⁻¹

Collisional energy transfer kinetics of vibrationally excited acetylene has been examined for states with internal energies near 6560 cm−1. Total population removal rate constants were determined for selected rotational levels of the (1,0,1,00,00) and (0,1,1,20,00) states. Values in the range of (10–18) × 10−10 cm3 s−1 were obtained. Measurements of state-to-state rotational energy transfer rate constants were also carried out for these states. The rotational energy transfer kinetics was found t...

Multireference configuration interaction calculations have been carried out for low-lying electronic states of AsH₂. Bending potentials for the ten lowest states of AsH₂ are obtained in C_2v symmetry for As–H distances fixed at the the ground state equilibrium value of 2.845 a₀, as well as for the minimum energy path constrained to R₁ = R₂. The calculated equilibrium geometries for the math

²B₁ ground state and the math

²A₁ excited state agree very well with the previous experimental and theoretical results, whereas the data for the higher-lying states are obtained for the first time. Asymmetric potential energy surface (PES) cuts (at R₁ = 2.845 a₀, θ = 90.7°) and two-dimensional (2D) PESs for the lowest three states are also new. The calculated ab initio data are used for analysis of possible AsH₂ photodissociation channels and predissociation effects. It is shown that the math

²A₁−

²B₁ transition dipole moment decreases with increasing bending angle, which influences the intensity distribution in the math

(0,0,0)→

emission spectrum (v2′′ bending series), shifting its maximum to smaller v2′′ quantum numbers.

Article Outline

INTRODUCTION
COMPUTATIONAL METHOD
RESULTS AND DISCUSSION
1. Bending potential energy curves
2. Asymmetric stretch potential energy curves
3. The ²A₁−²B₁ transition moment
CONCLUSION
ACKNOWLEDGMENTS

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KEYWORDS and PACS

Keywords

ab initio calculations, arsenic compounds, configuration interactions, excited states, ground states, molecular configurations, molecular moments, molecule-photon collisions, photodissociation, potential energy surfaces, predissociation, transition moments

PACS

31.15.am

Relativistic configuration interaction (CI) and many-body perturbation calculations
33.15.Bh

General molecular conformation and symmetry; stereochemistry
33.70.Ca

Oscillator and band strengths, lifetimes, transition moments, and Franck-Condon factors
33.15.Kr

Electric and magnetic moments (and derivatives), polarizability, and magnetic susceptibility
31.50.Df

Potential energy surfaces for excited electronic states
33.80.Gj

Diffuse spectra; predissociation, photodissociation

ARTICLE DATA

Digital Object Identifier

http://dx.doi.org/10.1063/1.3671374

PUBLICATION DATA

ISSN

0021-9606 (print)

1089-7690 (online)

Publisher

$abstract.society.value is a Member of CrossRef

American Institute of Physics

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