Ultrafast conformational dynamics of Rydberg-excited N-methyl piperidine

Du, Wenpeng; Gao, Yan; Stankus, Brian; Xu, Xuan; Yong, Haiwang; Weber, Peter M.

doi:10.1039/d1cp04236j

Ultrafast conformational dynamics of Rydberg-excited N-methyl piperidine

Journal Article · Wed Nov 24 00:00:00 EST 2021 · Physical Chemistry Chemical Physics. PCCP

DOI:https://doi.org/10.1039/d1cp04236j· OSTI ID:1862992

^[1]; Gao, Yan ^[2]; Stankus, Brian ^[3]; Xu, Xuan ^[2]; ^[4]; ^[2]

Brown Univ., Providence, RI (United States); Brown University
Brown Univ., Providence, RI (United States)
Western Connecticut State Univ., Danbury, CT (United States)
Brown Univ., Providence, RI (United States); Univ. of California, Irvine, CA (United States)

We have observed the ultrafast conformational dynamics of electronically excited N-methyl piperidine (NMP) using time-resolved Rydberg fingerprint spectroscopy. Optical excitation at various wavelengths ranging from 212 nm to 229 nm leads to the 3s or 3p Rydberg states and induces coherent oscillatory motions with periods of about 700 fs. Furthermore, these coherent motions survive the internal conversion from 3p to 3s but then dephase on a time scale of a few oscillations. Intramolecular vibrational energy redistribution on a picosecond time scale leads to an equilibrium between two conformeric structures that are separated in binding energy by 0.09 eV. Model calculations using the DFT-SIC method are in excellent agreement with the experiments and identify the conformers as the chair and twist structures of NMP. The analysis of the equilibrium parameters at long time delays as a function of excitation wavelength allows for the extraction of thermodynamic parameters for the conformeric transformation. We derive an enthalpy of the chair to twist reaction in the 3s excited state of 62 meV with an entropy of 19.70 J mol^–1 K^–1. An activation energy of 276 meV is also obtained with a kinetic model.

View Accepted Manuscript (DOE)

Research Organization:: Brown Univ., Providence, RI (United States)

Sponsoring Organization:: USDOE; USDOE Office of Science (SC), Basic Energy Sciences (BES)

Grant/Contract Number:: SC0017995

OSTI ID:: 1862992

Alternate ID(s):: OSTI ID: 1833869

Journal Information:: Physical Chemistry Chemical Physics. PCCP, Journal Name: Physical Chemistry Chemical Physics. PCCP Journal Issue: 48 Vol. 23; ISSN 1463-9076

Publisher:: Royal Society of ChemistryCopyright Statement

Country of Publication:: United States

Language:: English

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