Population Relaxation Research Articles

Dicyanamide Anion Reports on Water Induced Local Structural and Dynamic Heterogeneity in Ionic Liquid Mixtures.

The effects of limited amounts (under 21.6% χWater) of water on 1-butyl-3-methylimidazolium tetrafluoroborate (BmimBF4) and 1-butyl-3-methylimidazolium dicyanamide (BmimDCA) room-temperature ionic liquid (RTIL) mixtures were characterized by tracking changes in the linear and two-dimensional infrared (2D IR) vibrational features of the dicyanamide anion (DCA). Peak shifts with increasing water suggest the formation of water-associated and nonwater-associated DCA populations. Further results showed clear differences in the dynamic behavior of these different populations of DCA at low (defined here as below 2.5% χWater), mid (defined here as between 2.5% χWater and 9.6% χWater), and high (defined here as between 11.6% χWater and 21.6% χWater) range water concentrations. Vibrational relaxation is accelerated with increasing water content for water-associated populations of DCA, indicating water facilitates population relaxation, possibly through the provision of additional bath modes. Conversely, spectral diffusion of water-associated populations slowed dramatically with increasing water, suggesting that water drives the formation of distinct and noninterchangeable or very slowly interchangeable local solvent environments.

Spectrophotometric Concentration Analysis Without Molar Absorption Coefficients by Two-Dimensional-Infrared and Fourier Transform Infrared Spectroscopy.

A spectrophotometric method for determining relative concentrations of infrared (IR)-active analytes with unknown concentration and unknown molar absorption coefficient is explored. This type of method may be useful for the characterization of complex/heterogeneous liquids or solids, the study of transient species, and for other scenarios where it might be difficult to gain concentration information by other means. Concentration ratios of two species are obtained from their IR absorption and two-dimensional (2D)-IR diagonal bleach signals using simple ratiometric calculations. A simple calculation framework for deriving concentration ratios from spectral data is developed, extended to IR-pump-probe signals, and applied to the calculation of transition dipole ratios. Corrections to account for the attenuation of the 2D-IR signal caused by population relaxation, spectral overlap, wavelength-dependent pump absorption, inhomogeneous broadening, and laser intensity variations are described. A simple formula for calculating the attenuation of the 2D-IR signal due to sample absorption is deduced and by comparison with 2D-IR signals at varying total sample absorbance found to be quantitatively accurate. 2D-IR and Fourier transform infrared spectroscopy of two carbonyl containing species acetone and N-methyl-acetamide dissolved in D2O are used to experimentally confirm the validity of the ratiometric calculations. Finally, to address ambiguities over units and scaling of 2D-IR signals, a physical unit of 2D-IR spectral amplitude in mOD/ is proposed.

μ POP Clock: A Microcell Atomic Clock Based on a Double-Resonance Ramsey Scheme

We demonstrate and study a microcell microwave atomic clock based on optical-microwave double resonance (DR) interrogation operated in a pulsed Ramsey scheme, called the \ensuremath{\mu}POP clock, based on a microfabricated Rb vapor cell and a micro-loop-gap microwave resonator. For the mm-scale dimensions of this cell, the population and coherence relaxation rates of the Rb clock transition are on the order of 4--5 kHz, which puts constraints on the useful Ramsey times and overall pulse sequence in view of optimized clock performance. Our proof-of-principle demonstration of the \ensuremath{\mu}POP clock shows that the pulsed DR approach is nevertheless feasible and results in a short-term clock stability of 1 \ifmmode\times\else\texttimes\fi{} ${10}^{\ensuremath{-}11}$ \ensuremath{\tau}${}^{\ensuremath{-}1/2}$ and reaching the \ensuremath{\le}2 \ifmmode\times\else\texttimes\fi{} ${10}^{\ensuremath{-}12}$ level at timescales of 1000 s to one day. The short-term instability budget established for the \ensuremath{\mu}POP clock shows that the main limitation to the short-term stability arises from the detection noise. Thanks to the pulsed Ramsey scheme, light-shift effects are strongly reduced in the \ensuremath{\mu}POP clock, which opens perspectives for further improvements of long-term clock stability, in view of future generations of miniature vapor-cell clocks with enhanced performances based on the DR scheme.

Saturation Spectroscopic Studies on Yb3+ and Er3+ Ions in Li6Y(BO3)3 Single Crystals

The results of a series of pump–probe spectral hole-burning experiments are presented on Yb3+- or Er3+-doped Li6Y(BO3)3 (LYB) single crystals in the temperature range of 2–14 K and 9–28 K, respectively. The spectral hole has a complex structure for Yb3+ with superposed narrow and broad bands, while a single absorption hole has been observed for Er3+. Population relaxation times (T1) at about 850 ± 60 μs and 1010 ± 50 μs and dipole relaxation times (T2) with values of 1100 ± 120 ns and 14.2 ± 0.3 ns have been obtained for the two components measured for the Yb3+:2F7/2—2F5/2 transition. T1 = 402 ± 8 μs and T2 = 11.9 ± 0.2 ns values have been found for the Er3+:4I15/2—4I11/2 excitation. The spectral diffusion rate at about 1 and 5 MHz/ms has been determined for the narrow and broad spectral line in Yb3+-doped crystal, respectively. The temperature dependence of the spectral hole halfwidth has also been investigated.

Optical pumping and relaxation of atomic population in assorted conditions

Precise control and knowledge over atomic dynamics is central to the advancement of quantum technology. The different experimental conditions namely, atoms in a vacuum, antirelaxation coated and buffer gas filled atomic cells provide complementary platforms for such investigations. The extent of changes in optical pumping, velocity changing collision and hyperfine changing collision rates associated with these conditions are discussed. There is a phenomenal change in the optical density by a factor of >25 times in the presence of a control field in a buffer gas environment. We found confinement induced enhanced optical pumping as the mechanism behind the observed transparency in buffer gas cell. The diffusive velocity of atoms were measured to be ∼25 ± 12 m s−1 and ⩽8 ± 4 m s−1 for antirelaxation coated and buffer gas filled cells respectively. The measurements were carried out for 85Rb atoms in natural isotopic composition using pump–probe spectroscopy. The studies will have useful application in measurements of relaxation rates, quantum memory, quantum repeaters and atomic devices.

First observation and interpretation of spontaneous collective radiation from fusion-born ions in a stellarator plasma

During bursty MHD events, transient ion cyclotron emission (ICE) is observed from deuterium plasmas in the large helical device (LHD) heliotron-stellarator. Unusually, the frequencies of the successive ICE spectral peaks are not close to integer multiples of the local cyclotron frequency of an energetic ion population in the likely emitting region. We show that this ICE is probably driven by a subset of the fusion-born protons near their birth energy MeV. This subset has a kinetic energy component parallel to the magnetic field, , significantly greater than its perpendicular energy , for which , the Alfvén speed. First principles computations of the collective relaxation of this proton population, within a majority thermal deuterium plasma, are carried out using a particle-in-cell approach. This captures the full gyro-orbit kinetics of all ions which, together with an electron fluid, evolve self-consistently with the electric and magnetic fields under the Maxwell–Lorentz equations. The simulated ICE spectra are derived from the Fourier transform of the fields which are excited. We find substantial frequency shifts in the peaks of the simulated ICE spectra, which correspond closely to the measured ICE spectra following the resonance condition for nth proton harmonic. This suggests that the transient ICE in LHD is generated by the identified subset of the fusion-born protons, relaxing under the magnetoacoustic cyclotron instability. So far as is known, this is the first report of a collective radiation signal from fusion-born ions in anon-tokamak magnetically confined plasma. Disambiguation between two or more energetic ion species that could potentially generate complex observed ICE spectra is an increasing challenge, and the results and methodology developed here will assist this. Our approach is also expected to be relevant to ICE driven by ion beams with lower parallel velocities, for example in cylindrical plasma experiments.

Photon echo, spectral hole burning, and optically detected magnetic resonance inYb3+171:LiNbO3bulk crystal and waveguides

Recent progress in the realization of high-quality optical resonators and waveguides along with the possibility to incorporate rare-earth ions, make lithium niobate a promising material to build integrated platforms for quantum information processing. $^{171}\mathrm{Yb}^{3+}$ is a particularly attractive system because it can show long coherence lifetimes at zero magnetic field thanks to transitions insensitive to magnetic field fluctuations. In this paper, we investigate the optical and spin properties of $^{171}\mathrm{Yb}^{3+}$ ions in ${\mathrm{LiNbO}}_{3}$ bulk crystals as well as implanted waveguides. Using hole-burning spectroscopy and optically detected magnetic resonance, we studied ground and excited state hyperfine structures and probed optical and spin spectral holes. Importantly, the hole linewidths suggest that part of the ions in the waveguides are in a similar environment as in the bulk sample. We furthermore characterized spin population relaxation and coherence lifetimes of $^{171}\mathrm{Yb}^{3+}$ ions in the bulk crystal at temperatures between 50 mK and 9 K. At low temperatures, ${T}_{2}$ up to 9.5 $\ensuremath{\mu}\mathrm{s}$ (34 kHz homogeneous linewidth) and spin relaxation rates as long as $\ensuremath{\approx}100$ ms were measured. Our results show that $^{171}\mathrm{Yb}^{3+}$:$\mathrm{Li}\mathrm{Nb}{\mathrm{O}}_{3}$ is a system that exhibits narrow optical homogeneous linewidths over a 50 GHz bandwidth together with an electron spin degree of freedom. This is of interest for a variety of applications in integrated quantum photonics such as quantum memories or quantum processors.

Vibrational Dynamics of the Intramolecular H-Bond in Acetylacetone Investigated with Transient and 2D IR Spectroscopy.

Acetylacetone (AcAc) has proven to be a fruitful but highly challenging model system for the experimental and computational interrogation of strong intramolecular hydrogen bonds. Key questions remain, however, regarding the identity of the minimum-energy structure of AcAc and the dynamics of intramolecular proton transfer. Here, we investigate the OH/OD stretch and bend regions of the enol tautomer of AcAc and its deuterated isotopologue with transient absorption and 2D IR spectroscopy. The OH bend region reveals a single dominant diagonal transition near 1625 cm-1 with intense cross peaks to lower-frequency modes, demonstrating highly mixed fingerprint transitions that contain OH bend character. The anharmonic coupling of the OH bend results in a highly elongated OH bend excited-state absorption transition that indicates a large manifold of OH bend overtone/combination bands in the OH stretch region that leads to strong bend-stretch Fermi resonance interactions. The OH and OD stretch regions consist of broad ground-state bleach signals, but there is no clear evidence of ω21 excited-state absorptions due to rapid population relaxation arising from strong intramolecular coupling to bending, fingerprint, and low-frequency H-bond modes. Orientational relaxation dynamics persist for timescales longer than the vibrational lifetimes, with polarization anisotropy components decaying within approximately 2 and 10 periods of the O-O oscillation for the OH and OD stretch, respectively. The significant isotopic dependence of the orientational dynamics is discussed in the context of intramolecular mode coupling, diffusional processes, and contributions from proton/deuteron transfer dynamics.

Dynamics in tris(pentafluoroethyl)trifluorophosphate (FAP) anion based ionic liquids: A 2D-IR study with tungsten hexacarbonyl

Ultrafast two-dimensional infrared spectroscopy (2D-IR) measurements for tungsten hexacarbonyl, W(CO)6, has been performed in two fluoroalkylphosphate ([FAP])-based ultrahigh hydrophobic, ionic liquids, namely, 1-ethyl-3-methylimidazolium tris(pentafluoroethyl)-trifluorophosphate ([EMIM][FAP]) and 1-(hexyl)-3-methylimidazolium tris(pentafluoroethyl)trifluorophosphate ([HMIM][FAP]) to probe their local structure and dynamics. To understand the effect of FAP anion on the dynamics, a relatively less hydrophobic [PF6-] anion has been introduced in the form of [HMIM][PF6]. While the linear IR spectra records some influence of anion in terms of spectral shifts, the alkyl chain length of the cation seems to have no significant influence on the spectral peak position; and even the spectral broadening is found to be in the similar range. Further, vibrational population relaxation dynamics and vibrational anisotropy decay also does not show any significant variation due to difference in constituent of these ionic liquids as well as its solvent properties, such as, viscosity. Finally, 2D-IR spectra show large variation in the spectral shapes with waiting times, which qualitatively remains similar in all the tested ionic liquids. The frequency-fluctuation correlation function measured from 2D-IR spectra displays a bi-exponential decay with the shorter time-constant dependent on the identity of the anion, and has been attributed to the ion-rattling motion, whereas, the longer component has been found to be invariant with the identity of ionic liquid, and has been attributed to ion-cage motions which is in line with previous MD simulations as well as previous experimental measurements, using ionic vibrational probe. Overall, 2D-IR spectroscopy, in combination with this neutral and hydrophobic probe, W(CO)6 provides a unique opportunity to understand the local structural dynamics of this ultrahigh hydrophobic ionic liquid which are otherwise not accessible by hitherto explored ionic vibrational probes.

Tuning the adiabaticity of spin dynamics in diamond nitrogen vacancy centers

We study the spin dynamics of diamond nitrogen vacancy (NV) centers in an oscillating magnetic field along the symmetry axis of the NV in the presence of transverse magnetic fields. It is well-known that the coupling between the otherwise degenerate Zeeman levels |M S = ±1⟩ due to strain and electric fields is responsible for a Landau–Zener process near the pseudo-crossing of the adiabatic energy levels when the axial component of the oscillating magnetic field changes sign. We derive an effective two-level Hamiltonian for the NV system that includes coupling between the two levels via virtual transitions into the third far-detuned level |M S = 0⟩ induced by transverse magnetic fields. This coupling adds to the coupling due to strain and electric fields, with a phase that depends on the direction of the transverse field in the plane perpendicular to the NV axis. Hence, the total coupling of the Zeeman levels can be tuned to control the adiabaticity of spin dynamics by fully or partially compensating the effect of the strain and electric fields, or by enhancing it. Moreover, by varying the strength and direction of the transverse magnetic fields, one can determine the strength and direction of the local strain and electric fields at the position of the NV center, and even the external stress and electric field. The nuclear spin hyperfine interaction is shown to introduce a nuclear spin dependent offset of the axial magnetic field for which the pseudo-crossing occurs, while the adiabaticity remains unaffected by the nuclear spin. If the NV center is coupled to the environment, modeled by a bath with a Gaussian white noise spectrum, as appropriate for NVs near the diamond surface, then the spin dynamics is accompanied by relaxation of the Zeeman level populations and decoherence with a non-monotonic decrease of the purity of the system. The results presented here have important impact for metrology with NV centers, quantum control of spin systems in solids and coupled dynamics of spin and rotations in levitated nano-objects in the presence of magnetic fields.

Time-Domain Analysis of Chalcogenide Threshold Switching: From ns to ps Scale

A space- and time-dependent theoretical model based on a trap-assisted, charge-transport framework for the amorphous phase of a chalcogenide material is used here to interpret available experimental results for the electric current of nanoscale devices in the ns–ps time domain. A numerical solution of the constitutive equations of the model for a time-dependent bias has been carried out for GST-225 devices. The “intrinsic” rise time of the device current after the application of a suitable external bias is controlled by the microscopic relaxation of the mobile-carrier population to the steady-state value. Furthermore, the analysis is extended to include the effect of the external circuit on the electrical switching. A quantitative estimate of the current delay time due to unavoidable parasitic effects is made for the optimised electrical set up configurations recently used by experimental groups.

Structural Dynamics of Short Ligands on the Surface of ZnSe Semiconductor Nanocrystals.

ZnSe semiconductor nanocrystals (NCs) with a size comparable to their Bohr radius are synthesized, and the native capping agents with long hydrocarbon tails are replaced with short thiocyanate (SCN) ligands through a ligand exchange method. The structural dynamics of SCN ligands on the surface of ZnSe NCs in solution is investigated by ultrafast infrared spectroscopy. Vibrational population relaxation of SCN ligands is accelerated due to the specific interaction with the positively charged sites on the surface of NCs. The orientational anisotropy of the bound SCN ligands decayed at a rate much faster than that in the control solution containing Zn2+ cations. From the wobbling-in-the-cone model analysis, we found that the SCN ligand undergoes wobbling orientational diffusion with a relatively large cone semiangle on the surface of ZnSe NCs, and the overall orientational diffusion of bound SCN is found to be strongly dependent on the size of ZnSe NCs.

Femtosecond excited-state dynamics and ultrafast nonlinear optical investigations of ethynylthiophene functionalized porphyrin

Ethynylthiophene functionalized D-π-A porphyrin (LG5) belongs to a class of porphyrin molecules with proven application in organic solar cell devices. In this report, we present a comprehensive optical and non-linear optical characterization of ethynylthiophene functionalized porphyrin molecule, denoted as LG5. Femtosecond transient absorption (TA) spectroscopy was used to study the ultrafast excited-state properties with 400 nm, 70 fs photoexcitation. Global and target fitting analysis of the obtained TA spectra established a reliable photophysical model of excited state population relaxation and extracted the various rate constants. Considering the good performance of LG5 as a photosensitizer in dye-sensitized solar cells (DSSCs), electron injection studies on LG5 sensitized mesoporous TiO2 were also performed. Both integrated and transient photoluminescence (PL) data for LG5 sensitized TiO2 samples confirms efficient electron injection. The target analysis on TA data of LG5–TiO2 films revealed a multi-step electron injection from different excited energy levels with both ultrafast (≈370 fs) and slow injections times. Additionally, the non-linear optical (NLO) properties of LG5 are studied using the single-beam Z-scan technique upon photoexcitation of 800 nm, 70 fs laser pulses. The open aperture data demonstrated two-photon absorption (2PA), and closed aperture data indicated the presence of positive nonlinear refraction. The calculated values of 2PA cross-section and 3rd order NLO susceptibility were 1723 GM and 1.89 × 10−13 esu (2.64×10−21m2V−2), respectively.

Ultrafast vibrational dynamics of aqueous acetate and terephthalate

We study the vibrational population relaxation and mutual interaction of the symmetric stretch (νs) and antisymmetric stretch (νas) vibrations of the carboxylate anion groups of acetate and terephthalate ions in aqueous solution by femtosecond two-dimensional infrared spectroscopy. By selectively exciting and probing the νs and νas vibrations, we find that the interaction of the two vibrations involves both the anharmonic coupling of the vibrations and energy exchange between the excited states of the vibrations. We find that both the vibrational population relaxation and the energy exchange are faster for terephthalate than for acetate.

Vibrational dynamics of iron pentacarbonyl in cryogenic matrices.

Iron pentacarbonyl is a textbook example of fluxionality. We trap the molecule in cryogenic matrices to study the vibrational dynamics of CO stretching modes involved in the fluxional rearrangement. The infrared spectrum in Ar and N2 is composed of about ten narrow bands in the spectral range of interest, indicating the population of various lattice sites and a lowering of the molecular symmetry in the trapping sites. The vibrational dynamics is explored by means of infrared stimulated photon echoes at the femtosecond scale. Vibrational dephasing and population relaxation times are obtained. The non-linear signals exhibit strong oscillations useful to disentangle the site composition of the absorption spectrum. The population relaxation involves at least two characteristic times. An evolution of the photon echo signals with the waiting time is observed. The behavior of all the signals can be reproduced within a simple model that describes the population relaxation occurring in two steps: relaxation of v = 1 (population time T1 < 100ps) and return to v = 0 (recovery time > 1ns). These two steps explain the evolution of the oscillations with the waiting time in the photon echo signals. These results discard fluxional rearrangement on the time scale of hundreds of ps in our samples. Dephasing times are of the same order of magnitude as T1: dephasing processes due to the matrix environment are rather inefficient. The photon echo experiments also reveal that intermolecular resonant vibrational energy transfers between guest molecules occur at the hundreds of ps time scale in concentrated samples (guest/host > 104).

Coherent control and creation of population gratings for a pair of attosecond pulses in a resonant medium based on one-dimensional rectangular quantum wells

Attosecond pulses can be used to create and control coherence in resonant media, since their duration is shorter than the population relaxation times T1 and medium polarization T2. Previously, the possibility of creating and ultrafast control of electromagnetically induced gratings (EMIG) of atomic populations in a resonant medium was shown using a sequence of extremely short light pulses, when the pulses coherently interact with the medium and do not simultaneously overlap in the medium. These studies were carried out in various approximations, when a finite number of energy levels of the medium is taken into account, or when the pulse amplitude is small. In this paper, based on a direct numerical solution of the time dependent Schredinger equation without the indicated approximations, we study the possibility of ultrafast coherent control of populations and the creation of an EMIG by a pair of attosecond pulses in a multilevel resonant medium with a low density of particles. The medium is modeled using a one-dimensional rectangular potential well with infinitely high walls. The studies performed show the possibility of ultrafast coherent control of the properties of resonant media based on quantum wells using attosecond pulses. Keywords: electromagnetically induced gratings, coherent interaction, extremely short pulses, unipolar pulses, attosecond pulses, medium coherence.

Когерентное управление и создание решеток населенностей парой аттосекундных импульсов в резонансной среде на основе одномерных прямоугольных квантовых ям

Attosecond pulses can be used to create and control coherence in resonant media, since their duration is shorter than the population relaxation times T_1 and medium polarization T_2. Previously, the possibility of creating and ultrafast control of electromagnetically induced gratings (EMIG) of atomic populations in a resonant medium was shown using a sequence of extremely short light pulses, when the pulses coherently interact with the medium and do not simultaneously overlap in the medium. These studies were carried out in various approximations, when a finite number of energy levels of the medium is taken into account, or when the pulse amplitude is small. In this paper, based on a direct numerical solution of the time dependent Schrödinger equation without the indicated approximations, we study the possibility of ultrafast coherent control of populations and the creation of an EMIG by a pair of attosecond pulses in a multilevel resonant medium with a low density of particles. The medium is modeled using a one-dimensional rectangular potential well with infinitely high walls. The studies performed show the possibility of ultrafast coherent control of the properties of resonant media based on quantum wells using attosecond pulses.

Негармонические пространственные структуры разности населенностей, создаваемые униполярными прямоугольными импульсами в резонансной среде

In the case of coherent interaction with a medium of extremely short light pulses from a carrier of a harmonic form (when the pulse durations are shorter than the population relaxation times T_1 and polarization T_2 of the medium), electromagnetically induced gratings (EMIGs) of the population difference, which have a pronounced harmonic dependence on the coordinates, may appear in it. These structures can occur when pulses do not overlap at the same time or overlap in the medium. Recently, the possibility of obtaining unipolar electromagnetic pulses of the optical and adjacent ranges of non-harmonic shape, for example, rectangular and triangular, with a duration less than or comparable to the duration of the PCR in this range, has attracted interest. In this work, using the numerical solution of the system of Maxwell-Bloch equations, we study EMIG induced by rectangular attosecond pulses in a two-level resonant medium. The possibility of inducing an EMIG of a non-harmonic form in the form of light-induced channels, a kind of microresonators, with a size of the order of the wavelength of the resonant transition of the medium, whose parameters can be controlled, for example, by the amplitude of the incident pulses, is shown. It has been suggested that it is possible to create an EMIG of a predetermined non-harmonic form only in the general case of using unipolar pulses.

Nonharmonic Spatial Population Difference Structures Created by Unipolar Rectangular Pulses in a Resonant Medium

In the case of coherent interaction with a medium of extremely short light pulses (ESPs) having a carrier frequency and harmonic shape (when the pulse durations are shorter than the population relaxation times T1 and polarization relaxation time T2 of the medium), electromagnetically induced gratings (EMIGs) of the population difference, which have a pronounced harmonic dependence on the coordinates, may appear in it. These structures can occur when pulses do not overlap or overlap in the medium. Recently, the possibility of obtaining unipolar electromagnetic pulses in the optical and adjacent ranges of non-harmonic shape, for example, rectangular and triangular, with a duration less or comparable to the duration of the extremely-short pulse in this range, has attracted interest. In this work, using the numerical solution of the system of Maxwell-Bloch equations, we study EMIG formation by rectangular attosecond pulses in a two-level resonant medium. The possibility of inducing an EMIG of a non-harmonic shape in the form of light-induced channels microresonators, (microcavities) with a size of the order of the wavelength of the resonant transition of the medium, whose parameters can be controlled, for example, by the amplitude of the incident pulses, is shown. It has been suggested that it is possible to create an EMIG of a predetermined non-harmonic shape only in the general case of using unipolar pulses. Keywords: attosecond pulses, unipolar pulses, rectangular pulses, electromagnetically induced gratings, polarization waves, light-induced microresonators.

Phonon-Assisted Intervalley Scattering Determines Ultrafast Exciton Dynamics in MoSe_{2} Bilayers.

While valleys (energy extrema) are present in all band structures of solids, their preeminent role in determining exciton resonances and dynamics in atomically thin transition metal dichalcogenides (TMDC) is unique. Using two-dimensional coherent electronic spectroscopy, we find that exciton decoherence occurs on a much faster timescale in MoSe_{2} bilayers than that in the monolayers. We further identify two population relaxation channels in the bilayer, a coherent and an incoherent one. Our microscopic model reveals that phonon-emission processes facilitate scattering events from the K valley to other lower-energy Γ and Λ valleys in the bilayer. Our combined experimental and theoretical studies unequivocally establish different microscopic mechanisms that determine exciton quantum dynamics in TMDC monolayers and bilayers. Understanding exciton quantum dynamics provides critical guidance to the manipulation of spin-valley degrees of freedom in TMDC bilayers.