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The Journal of Physical Chemistry Letters

Long-Lived Electronic Coherence of Iodine in the Condensed Phase: Sharp Zero-Phonon Lines in the B↔X Absorption and Emission of I2 in Solid Xe

Eero Hulkko, Johan Lindgren, Toni Kiljunen, Mika Pettersson

Published Jun 20, 2012• 1 citation
Publisher

Abstract

Our study of B←X absorption of molecular iodine (I2) isolated in a low-temperature crystalline xenon has revealed an exceptionally long-lived electronic coherence in condensed phase conditions. The visible absorption spectrum shows prominent vibronic structure in the form of zero-phonon lines (ZPLs) and phonon side bands (PSBs). The resolved spectrum implies weak interaction of the chromophore to the lattice degrees of freedom. The coherence extends past the vibrational period of the excited state molecule, unlike that observed in any condensed phase environment for I2 so far. The ZP transitions from the relaxing B-state populations were resolved in the hot luminescence when the 532 nm laser was used for excitation.

DOI
10.1021/jz300651v

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Our study of B←X absorption of molecular iodine (I2) isolated in a low-temperature crystalline xenon has revealed an exceptionally long-lived electronic coherence in condensed phase conditions. The visible absorption spectrum shows prominent vibronic structure in the form of zero-phonon lines (ZPLs) and phonon side bands (PSBs). The resolved spectrum implies weak interaction of the chromophore to the lattice degrees of freedom. The coherence extends past the vibrational period of the excited state molecule, unlike that observed in any condensed phase environment for I2 so far. The ZP transitions from the relaxing B-state populations were resolved in the hot luminescence when the 532 nm laser was used for excitation.
The absorption spectrum of I2 in solid Xe shows resolved zero-phonon lines and phonon side bands near the origin of the B←X transition (550-625 nm). The long-lived |B⟩⟨X| coherence in this energy range (T2 = 600 fs on average) emerges as vibrationally unrelaxed fluorescence in resonance Raman (RR) spectra. Upon excitation in the structureless continuum at 532 nm, the oscillatory RR progression exhibits electronic dephasing time of T2 = 150 fs. Two RR progressions with markedly different vibrational coherence on the X-state are observed. The main progression of sharp overtones (T2 > 21 ps) is assigned to molecules trapped in double-substitution sites. The minor progression, which shows dephasing times T2 = 6-0.6 ps for v = 1-8, is assigned to molecules in triple-substitution sites. The line progressions allow a detailed characterization of the solvated B- and X-state potentials. Time-resolved coherent anti-Stokes Raman scattering is used to probe selected vibrational coherences on the X-state. Assignments are obtained through molecular dynamics simulations, which reproduce the relative dephasing rates between the two sites, clarify the role of rotation-translation dynamics, and enable quantum dynamics simulations of the spectra by the potentials of mean force that accurately describe the molecule-surrounding interactions.
Time-resolved, electronically resonant, coherent anti-Stokes Raman scattering is used to prepare and interrogate vibronic coherences of molecular iodine in matrix Ar. Coherences that involve evolution on the excited B(3Π0u) state, first- and third-order coherences, decay in less than one vibrational period (τ<300 fs). In contrast, as many as 200 vibrational periods of motion can be observed for Raman-prepared wave packets consisting of zero-phonon vibrational superpositions on the ground electronic state (second-order coherence). Packets consisting of v=4, 5 and v=3, 4, 5 on the X(1Σg) state decay with a half-life of 10±1 ps at 31 K, allowing a more accurate measure of vibrational level spacings and decoherence time than has been possible in frequency domain. The harmonic frequency of the molecule is reduced by 1.5 cm−1 (0.7%) in the matrix. The lack of recurrence in the excited electronic state ensures that the resonant anti-Stokes scattering arises only from the negative momentum component of the Raman packet. This momentum filter, which should be ubiquitous in condensed media, leads to a signal with deeper modulation than in the gas phase.
Time-resolved coherent anti-Stokes Raman-scattering (CARS) measurements are carried out for iodine (I2) in solid krypton matrices. The dependence of vibrational dephasing time on temperature and vibrational quantum number v is studied. The v dependence is approximately quadratic, while the temperature dependence of both vibrational dephasing and spectral shift, although weak, fits the exponential form characteristic of dephasing by pseudolocal phonons. The analysis of the data indicates that the frequency of the pseudolocal phonons is approximately 30 cm(-1). The longest dephasing times are observed for v = 2 being approximately 300 ps and limited by inhomogeneous broadening. An increase in the dephasing rate of v = 2 as the temperature is lowered to T = 2.6 K is taken as a clear indication of lattice-strain-induced inhomogeneity of the ensemble coherence.
Electronic and vibrational coherences of Cl2 embedded in solid Ar are investigated by exciting to the B state with a phase-locked pulse pair from an unbalanced Michelson interferometer, where the chirp difference matches the B state anharmonicity. Recording the A' --> X fluorescence after relaxation is compared to probing to charge transfer states by a third pulse. The three-pulse experiment delivers more details on the decoherence processes. The signal modulation due to phase tuning up to the third vibrational round-trip time indicates that the electronic coherence in the B <-- X transition is preserved for more than 660 fs in the solid Ar environment where many body electronic interactions take place. Vibrational coherence lasts longer than 3 ps according to the observed half revival of the wavepacket. Control of the coupling between wavepacket motion and lattice oscillation is demonstrated by tuning the relative phase between the phase-locked pulses, preparing wavepackets predominantly composed of either zero-phonon lines or phonon side bands.
We report the observation of ultralong coherence times in the purely electronic zero-phonon line emission of single terrylenediimide molecules at 1.4K. Vibronic excitation and spectrally resolved detection with a scanning Fabry–Perot spectrum analyzer were used to measure a linewidth of 65MHz. This is within a factor of 1.6 of the transform limit. It therefore indicates that single molecule emission may be suited for applications in linear optics quantum computation. Additionally, it is shown that high-resolution spectra taken with the spectrum analyzer allow for the investigation of fast spectral dynamics in the emission of a single molecule.
Time-resolved coherent anti-Stokes Raman scattering is applied to prepare and interrogate vibrational coherences on the ground electronic surface of molecular iodine isolated in Ar matrices. The coherence decay time shows a linear dependence on vibrational quantum numbers for v=3–15. The temperature dependence of decoherence rates is negligible for v<7 in the experimental range T=18–32 K. For a v=13, 14 superposition, the temperature dependence indicates dephasing by a 66 cm−1 pseudo-local phonon, just outside the Debye edge of the solid. The accuracy of the data is limited due to two-photon induced dissociation of the molecule, a process which is characterized using polarized fields. The T→0 limit of dephasing is discussed.