Coherence in nonradiative transitions: internal conversion in Rydberg-excited N-methyl and N-ethyl morpholine

Literature Information

Publication Date 2017-09-14
DOI 10.1039/C7CP05244H
Impact Factor 3.676
Authors

Yao Zhang, Peter M. Weber


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Abstract

The survival of coherent wavepacket motion during internal conversions is observed in relatively large molecules, N-methyl morpholine and N-ethyl morpholine, where standard models imply fast decoherence in a statistical limit. Optical excitation in the region of 194 to 230 nm excites the molecule to 3s or 3p Rydberg states, launching a wavepacket motion in the umbrella mode of the tertiary amine chromophore. In the short wavelength range, <214 nm, the molecules are excited to the 3p Rydberg state, which decays by internal conversion on a time scale of about 100 fs to the lower-lying 3s Rydberg state. Time-resolved photoionization photoelectron experiments reveal that the coherent wavepacket motion survives the internal conversion with oscillations continuing in the 3s state for several 650 fs periods before the phase lock is lost due to dephasing into the dense bath of vibrational modes of the molecule.

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Physical Chemistry Chemical Physics

Physical Chemistry Chemical Physics
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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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