Dynamics of molecular hydrogen elimination from the methaniminium cation, [CH2NH2]+.  Isotope effects, translational-energy release, and molecular-orbital calculations

Donchi, Kevin F.; Rumpf, Bruce A.; Willett, Gary D.; Christie, John; Derrick, Peter J.

doi:10.1021/ja00210a004

Cited by 31 publications

(8 citation statements)

References 2 publications

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“…Immediately after excitation, the system quickly decayed to the first excited state and subsequently to the ground state. Three main pathways were observed during the first 100 fs, in agreement with experimental observations and previous calculations: [77][78][79] Fast decay of fidelity F NAC , which can be seen in Fig. 2, demonstrates the vast importance of NACs in the quantum dynamics of photoexcited CH 2 NH 2 + .…”

Section: B On-the-fly Ab Initio Photoisomerization Dynamics Of Ch2nh2 +supporting

confidence: 89%

“…Immediately after excitation, when NACs were included in the dynamics, the system quickly decayed to the first excited state and subsequently to the ground state. Three main pathways were observed during the first 100 fs, in agreement with experimental observations and previous calculations: [77][78][79] (1) photoisomerization leading to the hot ground state CH 2 + , (2) bi-pyramidalisation leading to dissociation into CH 2 NH 2 + and NH 2 , and (3) release of H 2 . Fast decay of fidelity F NAC , which can be seen in Fig.…”

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confidence: 89%

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Evaluation of the importance of spin-orbit couplings in the nonadiabatic quantum dynamics with quantum fidelity and with its efficient “on-the-fly” ab initio semiclassical approximation

Zimmermann

Vaníček

2012

The Journal of Chemical Physics

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We propose to measure the importance of spin-orbit couplings (SOCs) in the nonadiabatic molecular quantum dynamics rigorously with quantum fidelity. To make the criterion practical, quantum fidelity is estimated efficiently with the multiple-surface dephasing representation (MSDR). The MSDR is a semiclassical method that includes nuclear quantum effects through interference of mixed quantumclassical trajectories without the need for the Hessian of potential energy surfaces. Two variants of the MSDR are studied, in which the nuclei are propagated either with the fewest-switches surface hopping or with the locally mean field dynamics. The fidelity criterion and MSDR are first tested on one-dimensional model systems amenable to numerically exact quantum dynamics. Then, the MSDR is combined with "on-the-fly" computed electronic structure to measure the importance of SOCs and nonadiabatic couplings in the photoisomerization dynamics of CH 2 NH + 2 considering 20 electronic states and in the collision of F + H 2 considering six electronic states.

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Section: B On-the-fly Ab Initio Photoisomerization Dynamics Of Ch2nh2 +supporting

confidence: 89%

supporting

confidence: 89%

Evaluation of the importance of spin-orbit couplings in the nonadiabatic quantum dynamics with quantum fidelity and with its efficient “on-the-fly” ab initio semiclassical approximation

Zimmermann

Vaníček

2012

The Journal of Chemical Physics

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“…After thermalization at 300 K in S 0 , the proton is transferred back, leading eventually to an isomerized product. Some trajectories also exhibit the experimentally observed H 2 abstraction [31].…”

Section: Fig 2 (Color) Evolution Of the State Populations (Upper Pamentioning

confidence: 69%

Trajectory Surface Hopping within Linear Response Time-Dependent Density-Functional Theory

2007

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A fewest switches trajectory surface hopping algorithm based on linear response time-dependent density-functional theory is developed and implemented into the plane wave ab initio molecular dynamics package CPMD. A scheme to calculate nonadiabatic couplings using a multi determinantal approximation of the excited state wave function is introduced. The method is applied to the study of the photorelaxation of protonated formaldimine, a minimal model of the rhodopsin chromophore retinal. A good agreement of the structural and dynamic behavior is found with respect to state averaged multiconfiguration self consistent field based trajectory surface hopping.

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“…3 Derrick and co-workers 9 presented a method to predict the average KER in a dissociation reaction by considering atomic motions constituting the reaction coordinate at the transition state. Although the method has been found to be successful to explain the isotope effect on KER for some systems, 10,11 this is expected to be useful only when a good overlap between the reaction coordinate and the product separation coordinate is maintained throughout the exit channel. 12 In general cases, however, detailed consideration of the interaction along the exit channel is needed, which requires a dynamical approach.…”

Section: Introductionmentioning

confidence: 99%

Dynamic isotope effect on the product energy partitioning in CH2OH+→CHO++H2

Rhee

Kim

1998

The Journal of Chemical Physics

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Dynamics of molecular hydrogen elimination from the methaniminium cation, [CH2NH2]+. Isotope effects, translational-energy release, and molecular-orbital calculations

Cited by 31 publications

References 2 publications

Evaluation of the importance of spin-orbit couplings in the nonadiabatic quantum dynamics with quantum fidelity and with its efficient “on-the-fly” ab initio semiclassical approximation

Evaluation of the importance of spin-orbit couplings in the nonadiabatic quantum dynamics with quantum fidelity and with its efficient “on-the-fly” ab initio semiclassical approximation

Trajectory Surface Hopping within Linear Response Time-Dependent Density-Functional Theory

Dynamic isotope effect on the product energy partitioning in CH2OH+→CHO++H2

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