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Two-Dimensional Electronic Spectroscopy Resolves Relative Excited-State Displacements.

ABSTRACT: Knowledge of relative displacements between potential energy surfaces (PES) is critical in spectroscopy and photochemistry. Information on displacements is encoded in vibrational coherences. Here we apply ultrafast two-dimensional electronic spectroscopy in a pump-probe half-broadband (HB2DES) geometry to probe the ground- and excited-state potential landscapes of cresyl violet. 2D coherence maps reveal that while the coherence amplitude of the dominant 585 cm^-1 Raman-active mode is mainly localized in the ground-state bleach and stimulated emission regions, a 338 cm^-1 mode is enhanced in excited-state absorption. Modeling these data with a three-level displaced harmonic oscillator model using the hierarchical equation of motion-phase matching approach (HEOM-PMA) shows that the S₁ ← S₀ PES displacement is greater along the 585 cm^-1 coordinate than the 338 cm^-1 coordinate, while S_n ← S₁ displacements are similar along both coordinates. HB2DES is thus a powerful tool for exploiting nuclear wavepackets to extract quantitative multidimensional, vibrational coordinate information across multiple PESs.

SUBMITTER: Bressan G

PROVIDER: S-EPMC10945572 | biostudies-literature | 2024 Mar

REPOSITORIES: biostudies-literature

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Two-Dimensional Electronic Spectroscopy Resolves Relative Excited-State Displacements.

Bressan Giovanni G Green Dale D Jones Garth A GA Heisler Ismael A IA Meech Stephen R SR

The journal of physical chemistry letters 20240306 10

Knowledge of relative displacements between potential energy surfaces (PES) is critical in spectroscopy and photochemistry. Information on displacements is encoded in vibrational coherences. Here we apply ultrafast two-dimensional electronic spectroscopy in a pump-probe half-broadband (HB2DES) geometry to probe the ground- and excited-state potential landscapes of cresyl violet. 2D coherence maps reveal that while the coherence amplitude of the dominant 585 cm<sup>-1</sup> Raman-active mode is m ...[more]

PMID: 38447068

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Project description:The theory of electronic structure of many-electron systems, such as molecules, is extraordinarily complicated. A consideration of how electron density is distributed on average in the average field of the other electrons in the system, that is, mean field theory, is very instructive. However, quantitatively describing chemical bonds, reactions, and spectroscopy requires consideration of the way that electrons avoid each other while moving; this is called electron correlation (or in physics, the many-body problem for fermions). Although great progress has been made in theory, there is a need for incisive experimental tests for large molecular systems in the condensed phase. In this Account, we report a two-dimensional (2D) optical coherent spectroscopy that correlates the double-excited electronic states to constituent single-excited states. The technique, termed 2D double-quantum coherence spectroscopy (2D-DQCS), uses multiple, time-ordered ultrashort coherent optical pulses to create double- and single-quantum coherences over time intervals between the pulses. The resulting 2D electronic spectrum is a map of the energy correlation between the first excited state and two-photon allowed double-quantum states. The underlying principle of the experiment is that when the energy of the double-quantum state, viewed in simple models as a double HOMO-to-LUMO (highest occupied to lowest unoccupied molecular orbital) excitation, equals twice that of a single excitation, then no signal is radiated. However, electron-electron interactions, a combination of exchange interactions and electron correlation, in real systems generates a signal that reveals precisely how the energy of the double-quantum resonance differs from twice the single-quantum resonance. The energy shift measured in this experiment reveals how the second excitation is perturbed by both the presence of the first excitation and the way that the other electrons in the system have responded to the presence of that first excitation. We compare a series of organic dye molecules and find that the energy offset for adding a second electronic excitation to the system relative to the first excitation is on the order of tens of millielectronvolts; it also depends quite sensitively on molecular geometry. These results demonstrate the effectiveness of 2D-DQCS for elucidating quantitative information about electron-electron interactions, many-electron wave functions, and electron correlation in electronic excited states and excitons. Our work helps illuminate the implications of electron correlation on chemical systems. In a broad sense, we are trying to help address the fundamental question "How do we go beyond the orbital representation of electrons in the chemical sciences?"

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Two-Dimensional Electronic Spectroscopy Resolves Relative Excited-State Displacements.

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Two-Dimensional Electronic Spectroscopy Resolves Relative Excited-State Displacements.

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