Photodissociation dynamics of trimethyltin iodide

Amor, Nadia Ben; Ambrosek, David; Daniel, Chantal; Marquardt, Roberto

doi:10.1016/j.chemphys.2007.05.029

Cited by 10 publications

(3 citation statements)

References 38 publications

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“…Such a PES may be called post-spin-orbit (SO) adiabatized. Post-SO-adiabatic potential energy curves have been used in the description of the photodissociation of trimethyltiniodide …”

Section: Resultsmentioning

confidence: 99%

Global Analytical Potential Energy Surface for the Electronic Ground State of NH₃ from High Level ab Initio Calculations

et al. 2013

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The analytical, full-dimensional, and global representation of the potential energy surface of NH(3) in the lowest adiabatic electronic state developed previously (Marquardt, R.; et al. J. Phys. Chem. B 2005, 109, 8439–8451) is improved by adjustment of parameters to an enlarged set of electronic energies from ab initio calculations using the coupled cluster method with single and double substitutions and a perturbative treatment of connected triple excitations (CCSD(T)) and the method of multireference configuration interaction (MRCI). CCSD(T) data were obtained from an extrapolation of aug-cc-pVXZ results to the basis set limit (CBS), as described in a previous work (Yurchenko, S.N.; et al. J. Chem. Phys 2005, 123, 134308); they cover the region around the NH3 equilibrium structures up to 20,000 hc cm(–1). MRCI energies were computed using the aug-cc-pVQZ basis to describe both low lying singlet dissociation channels. Adjustment was performed simultaneously to energies obtained from the different ab initio methods using a merging strategy that includes 10,000 geometries at the CCSD(T) level and 500 geometries at the MRCI level. Characteristic features of this improved representation are NH3 equilibrium geometry r(eq)(NH(3)) ≈ 101.28 pm, α(eq)(NH(3)) ≈ 107.03°, the inversion barrier at r(inv)(NH(3)) ≈ 99.88 pm and 1774 hc cm(–1) above the NH(3) minimum, and dissociation channel energies 41,051 hc cm(–1) (for NH(3) → ((2)B(2))NH(2) + ((2)S(1/2))H) and 38,450 hc cm(–1) (for NH(3) → ((3)Σ(–))NH +((1)Σ(g)(+))H(2)); the average agreement between calculated and experimental vibrational line positions is 11 cm(–1) for (14)N(1)H(3) in the spectral region up to 5000 cm(–1). A survey of our current knowledge on the vibrational spectroscopy of ammonia and its isotopomers is also given.

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“…Such a PES may be called post-spin-orbit (SO) adiabatized. Post-SO-adiabatic potential energy curves have been used in the description of the photodissociation of trimethyltiniodide …”

Section: Resultsmentioning

confidence: 99%

Global Analytical Potential Energy Surface for the Electronic Ground State of NH₃ from High Level ab Initio Calculations

et al. 2013

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“…On the basis of several simulations, it is shown that the efficiency of the singlet-triplet intersystem crossing does not depend only on the SOC values but also drastically on the available kinetic energy of the wave packet (induced by the potential shifts) when approaching the singlet-triplet crossing. Further work should be devoted to a refinement of the PES by performing more accurate ab initio calculations 9 and to an improvement of our model by including other nuclear relaxation effects in the electronic excited states. 10 Despite the complexity of the electronic problem, we have shown that the photoreactivity of MTO at the early stage (before 0.5 ps) is governed by the dynamics of only three excited states, the b 1 A 1 absorbing state, the near a 1 E state (both bound and corresponding to excitation from the p O oxygen lone pairs to a p* ReO metal centred orbital), and the a 3 A 1 dissociative state.…”

Section: Discussionmentioning

confidence: 99%

Photoinduced bond cleavage in CH3ReO3: excited state dynamics

2008

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“…Having established that conical intersections are accessible to connect excited state with ground-state potential energy surfaces, the next stage in modeling the reactive photochemistry is to simulate the dynamical motion of the nuclei on those coupled potential energy surfaces. Guillaumont [et al] [104] performed a large number of dynamics simulations in inorganic photochemistry using quantum wave packet approaches [104][105][106]. The majority of these studies used one-or twodimensional simulations that are appropriate for studying phenomena such as direct photodissociation [78].…”

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confidence: 99%

STRUCTURAL DYNAMICS OF FREE MOLECULES AND CONDENSED STATE OF MATTER. Part II. TRANSIENT STRUCTURES IN CHEMICAL REACTIONS

2017

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Basic knowledge of mankind so far relates to the description of electrons and atoms in the material in a state of equilibrium, where the behavior changes slowly over time. The electron diffraction with a high temporal and space resolution has opened the possibility of direct observation of the processes occurring in the transient state of the substance (molecular movie). Here it is necessary to provide a temporary resolution of the order of 100 fs, which corresponds to the transition of the system through the energy barrier of the potential surface, which describes the chemical reaction - the process of the breaking and the formation of new bonds between the interacting agents. Thus, the possibility of the investigation of the coherent nuclear dynamics of molecular systems and the condensed matter can be opened. In the past two decades, it has been possible to observe the nuclear motion in the temporal interval corresponding to the period of the nuclear oscillation. The observed coherent changes in the nuclear system at such temporal intervals determine the fundamental shift from the standard kinetics of chemical reactions to the dynamics of the phase trajectory of a single molecule, the molecular quantum state tomography.

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Photodissociation dynamics of trimethyltin iodide

Cited by 10 publications

References 38 publications

Global Analytical Potential Energy Surface for the Electronic Ground State of NH₃ from High Level ab Initio Calculations

Global Analytical Potential Energy Surface for the Electronic Ground State of NH₃ from High Level ab Initio Calculations

Photoinduced bond cleavage in CH3ReO3: excited state dynamics

STRUCTURAL DYNAMICS OF FREE MOLECULES AND CONDENSED STATE OF MATTER. Part II. TRANSIENT STRUCTURES IN CHEMICAL REACTIONS

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Photodissociation dynamics of trimethyltin iodide

Cited by 10 publications

References 38 publications

Global Analytical Potential Energy Surface for the Electronic Ground State of NH3 from High Level ab Initio Calculations

Global Analytical Potential Energy Surface for the Electronic Ground State of NH3 from High Level ab Initio Calculations

Photoinduced bond cleavage in CH3ReO3: excited state dynamics

STRUCTURAL DYNAMICS OF FREE MOLECULES AND CONDENSED STATE OF MATTER. Part II. TRANSIENT STRUCTURES IN CHEMICAL REACTIONS

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Global Analytical Potential Energy Surface for the Electronic Ground State of NH₃ from High Level ab Initio Calculations

Global Analytical Potential Energy Surface for the Electronic Ground State of NH₃ from High Level ab Initio Calculations