N–H photodissociation dynamics of electronically excited aniline: a three dimensional time-dependent quantum wavepacket study
文献信息
Jyotirmoy Ray, Sai G. Ramesh
We have simulated the dynamics of 1πσ* state-mediated nonadiabatic N–H bond dissociation in photo-excited aniline (C6H5NH2). A three electronic state diabatic model potential, involving the ground, 1ππ*, and 1πσ* diabatic states, and focussing on the NH2 degrees of freedom alone is constructed using XMS-CASPT2 energies. Using a kinetic energy operator in the polyspherical framework, wavepacket dynamics in three vibrational modes, viz. NH stretch, NH2 out-of-plane wag and torsion, is carried out using the Chebyshev propagation scheme. For optically bright 1ππ* excitation, the wavepacket can access the 1πσ*/1ππ* and 1ππ/1πσ* conical intersections that lie en route to dissociation. For both intersections, NH2 out-of-plane wag and torsional motions are the most dominant coupling coordinates. Carrying out dynamics with initial wavepackets varying in excitation in the three degrees of freedom, we probe their roles in the evolution of the state populations, probability densities, and product branching for the NH dissociation process.
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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics (PCCP) is an international journal co-owned by 19 physical chemistry and physics societies from around the world. This journal publishes original, cutting-edge research in physical chemistry, chemical physics and biophysical chemistry. To be suitable for publication in PCCP, articles must include significant innovation and/or insight into physical chemistry; this is the most important criterion that reviewers and Editors will judge against when evaluating submissions. The journal has a broad scope and welcomes contributions spanning experiment, theory, computation and data science. Topical coverage includes spectroscopy, dynamics, kinetics, statistical mechanics, thermodynamics, electrochemistry, catalysis, surface science, quantum mechanics, quantum computing and machine learning. Interdisciplinary research areas such as polymers and soft matter, materials, nanoscience, energy, surfaces/interfaces, and biophysical chemistry are welcomed if they demonstrate significant innovation and/or insight into physical chemistry. Joined experimental/theoretical studies are particularly appreciated when complementary and based on up-to-date approaches.




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