Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state

Gourab Chatterjee; Ajay Jha; Alejandro Blanco-Gonzalez; Vandana Tiwari; Madushanka Manathunga; Hong-Guang Duan; Friedjof Tellkamp; Valentyn I. Prokhorenko; Nicolas Ferré; Jyotishman Dasgupta; Massimo Olivucci; R. J. Dwayne Miller

doi:10.1039/D2SC02133A

Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state†

Gourab Chatterjee,

‡§^a Ajay Jha,

¶§^a Alejandro Blanco-Gonzalez,

§^b Vandana Tiwari,

^ac Madushanka Manathunga,^b Hong-Guang Duan,^a Friedjof Tellkamp,^a Valentyn I. Prokhorenko,^a Nicolas Ferré,

^d Jyotishman Dasgupta,

^e Massimo Olivucci

*^bf and R. J. Dwayne Miller

*^g

Author affiliations

* Corresponding authors

^a Max Planck Institute for the Structure and Dynamics of Matter, Luruper Chaussee 149, 22761 Hamburg, Germany

^b Department of Chemistry, Bowling Green State University, Bowling Green, OH, USA
E-mail: olivucci@unisi.it

^c Department of Chemistry, University of Hamburg, Martin-Luther-King Platz 6, 20146 Hamburg, Germany

^d Aix-Marseille Univ, CNRS, ICR, 13013 Marseille, France

^e Department of Chemical Sciences, Tata Institute of Fundamental Research, Mumbai, India

^f Dipartimento di Biotechnologie, Chimica e Farmacia, Università di Siena, Siena, Italy

^g Departments of Chemistry and Physics, University of Toronto, 80 St. George Street, Toronto M5S 3H6, Canada
E-mail: dmiller@lphys.chem.utoronto.ca

Abstract

The concerted interplay between reactive nuclear and electronic motions in molecules actuates chemistry. Here, we demonstrate that out-of-plane torsional deformation and vibrational excitation of stretching motions in the electronic ground state modulate the charge-density distribution in a donor-bridge-acceptor molecule in solution. The vibrationally-induced change, visualised by transient absorption spectroscopy with a mid-infrared pump and a visible probe, is mechanistically resolved by ab initio molecular dynamics simulations. Mapping the potential energy landscape attributes the observed charge-coupled coherent nuclear motions to the population of the initial segment of a double-bond isomerization channel, also seen in biological molecules. Our results illustrate the pivotal role of pre-twisted molecular geometries in enhancing the transfer of vibrational energy to specific molecular modes, prior to thermal redistribution. This motivates the search for synthetic strategies towards achieving potentially new infrared-mediated chemistry.

Chemical Science

Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state†

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Torsionally broken symmetry assists infrared excitation of biomimetic charge-coupled nuclear motions in the electronic ground state

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