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Abstract The complex choreography of electronic, vibrational, and vibronic couplings used by photoexcited molecules to transfer energy efficiently is remarkable, but an unambiguous description of the temporally evolving vibronic states governing these processes has proven experimentally elusive. We use multidimensional electronic-vibrational spectroscopy to identify specific time-dependent excited state vibronic couplings involving multiple electronic states, high-frequency vibrations, and low-frequency vibrations which participate in ultrafast intersystem crossing and subsequent relaxation of a photoexcited transition metal complex. We discover an excited state vibronic mechanism driving long-lived charge separation consisting of an initial electronically-localized vibrational wavepacket which triggers delocalization onto two charge transfer states after propagating for ~600 femtoseconds. Electronic delocalization consequently occurs through nonadiabatic internal conversion driven by a 50 cm−1coupling resulting in vibronic coherence transfer lasting for ~1 picosecond. This study showcases the power of multidimensional electronic-vibrational spectroscopy to elucidate complex, non-equilibrium energy and charge transfer mechanisms involving multiple molecular coordinates.
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From Coherence to Function: Exploring the Connection in Chemical Systems
Conspectus: The role of quantum mechanical coherences or coherent superposition states in excited state processes has received considerable attention in the last two decades largely due to advancements in ultrafast laser spectroscopy. These coherence effects hold promise for enhancing the efficiency and robustness of functionally relevant processes, even when confronted with strong energy disorder and environmental fluctuations. Understanding coherence deeply drives us to unravel mechanisms and dynamics controlled by order and synchronization at a quantum mechanical level, envisioning optical control of coherence to enhance functions or create new ones in molecular and material systems. In this frontier, the interplay between electronic and vibrational dynamics, specifically the influence of vibrations in directing electronic dynamics, has emerged as the leading principle. Here, two energetically disparate quantum degrees of freedom work in-sync to dictate the trajectory of an excited state reaction. Moreover, with the vibrational degree being directly related to the structural composition of molecular or material systems, new molecular designs could be inspired by tailoring certain structural elements. In the realm of chemical kinetics, our understanding of the dynamics of chemical transformations is underpinned by fundamental theories such as transition state theory, activated rate theory, and Marcus theory. These theories elucidate reaction rates by considering the energy barriers that must be overcome for reactants to transform into products. Those barriers are surmounted by the stochastic nature of energy gap fluctuations within reacting systems, emphasizing that the reaction coordinate—the pathway from reactants to products—is not rigidly defined by a specific vibrational motion but encompasses a diverse array of molecular motions. While less is known about the involvement of specific intramolecular vibrational modes, their significance in certain cases cannot be overlooked. In this Account, we summarize key experimental findings that offer deeper insights into the complex electronic-vibrational trajectories encompassing excited states afforded from state-of-the-art ultrafast laser spectroscopy in three exemplary processes: photo-induced electron transfer, singlet-triplet intersystem crossing, and intramolecular vibrational energy flow in molecular systems. We delve into rapid decoherence—loss of phase and amplitude correlations—of vibrational coherences along promoter vibrations during a sub-picosecond intersystem crossing dynamics in a series of binuclear platinum complexes. This rapid decoherence illustrates the vibration-driven reactive pathways from Franck-Condon state to the curve crossing region. We also explore the generation of new vibrational coherences induced by impulsive reaction dynamics—rather than by the laser pulse—in these systems, which sheds light on specific energy dissipation pathways and thereby on the progression of the reaction trajectory in the vicinity of the curve crossing on the product side. Another property of vibrational coherences, amplitude, reveals how energy can flow from one vibration to another in the electronic excited state of a terpyridine-molybdenum complex hosting a nonreactive dinitrogen substrate. A slight change in vibrational energy triggers a quasi-resonant interaction, leading to constructive wavepacket interference and ultimately intramolecular vibrational redistribution from a Franck-Condon active terpyridine vibration to dinitrogen stretching vibration, energizing the dinitrogen bond.
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- Award ID(s):
- 2247821
- PAR ID:
- 10625574
- Publisher / Repository:
- American Chemical Society
- Date Published:
- Journal Name:
- Accounts of Chemical Research
- Volume:
- 57
- Issue:
- 18
- ISSN:
- 0001-4842
- Page Range / eLocation ID:
- 2620 to 2630
- Format(s):
- Medium: X
- Sponsoring Org:
- National Science Foundation
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- Free Publicly Accessible Full Text
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Accepted Manuscript1.0
- Journal Article:
- https://doi.org/10.1021/acs.accounts.4c00312
