Fast Spectral Diffusion Research Articles

Investigating the fast spectral diffusion of a quantum emitter in hBN using resonant excitation and photon correlations

The ability to identify and characterize homogeneous and inhomogeneous dephasing processes is crucial in solid-state quantum optics. In particular, spectral diffusion leading to line broadening is difficult to evidence when the associated timescale is shorter than the inverse of the photon detection rate. Here, we show that a combination of resonant laser excitation and second-order photon correlations allows to access such fast dynamics. The resonant laser drive converts spectral diffusion into intensity fluctuations, leaving a signature in the second-order coherence function $g^{(2)}(\tau)$ of the scattered light that can be characterized using two-photon coincidences -- which simultaneously provides the homogeneous dephasing time. We experimentally implement this method to investigate the fast spectral diffusion of a color center generated by an electron beam in the two-dimensional material hexagonal boron nitride. The $g^{(2)}(\tau)$ function of the quantum emitter measured over more than ten orders of magnitude of delay times, at various laser powers, establishes that the color center experiences spectral diffusion at a characteristic timescale of a few tens of microseconds, while emitting Fourier-limited single photons ($T_2/2T_1 \sim 1$) between spectral jumps.

Two-dimensional infrared spectral explorations into bilayer and monolayer self-assemblies of amphiphilic polypeptides

Poly(2-(3-((2-hydroxyethyl)amino)-3-oxopropyl)ethyleneamido) (PHAOE) is an amphiphilic polypeptide. The self-assembly is significant, but the ultrafast dynamic analyses of the peptide self-assembly are exiguous and worth further exploring. In this investigation, the temporal dynamic characteristics of the aggregates and unaggregated PHAOEs are mined by the two-dimensional infrared (2D IR) spectroscopy. The homogeneous and inhomogeneous diffusion processes of the carbonyl stretching modes of the unaggregated PHAOEs are slower than those of the self-assemblies. The inhomogeneous spectral diffusion proportion of the biopolymer PHAOE in methanol is greater than that in dimethyl sulfoxide (DMSO). The solvation shells surround the aggregates and unaggregated PHAOEs in the protic solvent methanol, but there are not any solvation shells around the aggregates or unaggregated PHAOEs in the dipolar solvent DMSO. The massive hydrogen-bonded monolayer self-assembly has merely an aggregate of PHAOEs and no solvation shell in DMSO. But the hydrogen-bonded bilayer self-assembly has a self-assembled methanol shell and an interior aggregate of PHAOEs in methanol. The self-assemblies of PHAOEs motivate the methanols to self-assemble. The large delocalized amide structure results in the fast spectral diffusion of the carbonyl stretching mode.Communicated by Ramaswamy H. Sarma

Two dimensional infrared spectroscopic investigations of protein and enzyme dynamics

Ultra fast two dimensional infrared (2D IR) spectroscopy is used to measure dynamics and interactions in complex materials in the ground electronic state under thermal equilibrium conditions. Two observables, ultra fast chemical exchange and spectral diffusion, will be discussed. In a 2D IR experiment, three variably time delayed IR excitation pulses, tuned to the vibrational transition of interest, give rise to a fourth vibrational echo pulse, the signal in the experiment. The first two pulses in the sequence label the vibrations with their initial frequencies. After a waiting period, Tw, the third pulse induces the vibrational echo, which reads out the final vibrational frequencies. Structural changes of the system cause the vibrational frequencies to change. Therefore, measuring the time evolution of the vibrational frequencies reports on the time evolution of the structure. Folded proteins can exist in multiple conformational substates. Each substate reflects a local minimum on the free‐energy landscape with a distinct structure. Using 2D‐IR chemical exchange spectroscopy, conformational switching between two well defined substates of two myoglobin mutants were observed on the ~50 ps time scale. The conformational dynamics were measured through the growth of off‐diagonal peaks in the 2D IR spectra of CO bound to the heme. The conformational switching likely involves motion of the distal histidine/E helix that changes the position of the histidine's imidazole side group. These results demonstrate that interconversion between protein conformational substates can occur on very fast time scales. Detailed MD simulations are able to capture some of the observed behavior, but not quantitatively. Cytochrome (cyt) P450s hydroxylate a variety of substrates that can differ widely in their chemical structure. The importance of these enzymes in drug metabolism and other biological processes has motivated the study of the factors that enable their activity on diverse classes of molecules. 2D IR spectroscopy was used to measure the dynamics of cyt P450cam from Pseudomonas putida using CO bound at the active site as the vibrational probe. The experiments measure spectral diffusion, the time evolution of the CO vibrational frequencies within the in homogeneously broadened vibrational absorption line. The time evolution of the frequencies is caused by the time evolution of the enzyme structure. The enzyme bound to both its natural substrate, camphor, and a series of related substrates were investigated to explicate the role of dynamics in molecular recognition in cyt P450cam and to delineate how the motions may contribute to hydroxylation specificity. Correlations in the observed dynamics with the specificity of hydroxylation of the substrates, the binding affinity, and the substrates' molecular volume suggest that motions on the hundreds of picosecond time scale contribute to the variation in activity of cyt P450cam toward different substrates.This abstract is from the Experimental Biology 2018 Meeting. There is no full text article associated with this abstract published in The FASEB Journal.

Picosecond Proton Transfer Kinetics in Water Revealed with Ultrafast IR Spectroscopy.

Aqueous proton transport involves the ultrafast interconversion of hydrated proton species that are closely linked to the hydrogen bond dynamics of water, which has been a long-standing challenge to experiments. In this study, we use ultrafast IR spectroscopy to investigate the distinct vibrational transition centered at 1750 cm-1 in strong acid solutions, which arises from bending vibrations of the hydrated proton complex. Broadband ultrafast two-dimensional IR spectroscopy and transient absorption are used to measure vibrational relaxation, spectral diffusion, and orientational relaxation dynamics. The hydrated proton bend displays fast vibrational relaxation and spectral diffusion timescales of 200-300 fs; however, the transient absorption anisotropy decays on a remarkably long 2.5 ps timescale, which matches the timescale for hydrogen bond reorganization in liquid water. These observations are indications that the bending vibration of the aqueous proton complex is relatively localized, with an orientation that is insensitive to fast hydrogen bonding fluctuations and dependent on collective structural relaxation of the liquid to reorient. We conclude that the orientational relaxation is a result of proton transfer between configurations that are well described by a Zundel-like proton shared between two flanking water molecules.

Spectral diffusion and dynamic nuclear polarization: Beyond the high temperature approximation

Dynamic Nuclear Polarization (DNP) has proven itself most powerful for the orientation of nuclear spins in polarized targets and for hyperpolarization in magnetic resonance imaging (MRI). Unfortunately, the theoretical description of some of the processes involved in DNP invokes the high temperature approximation, in which Boltzmann factors are expanded up to first order, while the high electron and nuclear spin polarization required for many applications do not justify such an approximation. A previous article extended the description of one of the mechanisms of DNP—thermal mixing—beyond the high temperature approximation (Wenckebach, 2017). But that extension is still limited: it assumes that fast spectral diffusion creates a local equilibrium in the electron spin system.Provotorov’s theory of cross-relaxation enables a consistent further extension to slower spectral diffusion, but also invokes the high temperature approximation. The present article extends the theory of cross-relaxation to low temperature and applies it to spectral diffusion in glasses doped with paramagnetic centres with anisotropic g-tensors. The formalism is used to describe DNP via the mechanism of the cross effect. In the limit of fast spectral diffusion the results converge to those obtained in Wenckebach (2017) for thermal mixing. In the limit of slow spectral diffusion a hole is burnt in the electron spin resonance (ESR) signal, just as predicted by more simple models. The theory is applied to DNP of proton and 13C spins in samples doped with the radical TEMPO.

A First-Principles Molecular Dynamics Study of the Solvation Shell Structure, Vibrational Spectra, Polarity, and Dynamics around a Nitrate Ion in Aqueous Solution.

A first-principles molecular dynamics study is presented for the structural, dynamical, vibrational, and dipolar properties of the solvation shell of a nitrate ion in deuterated water. A detailed description of the anisotropic structure of the solvation shell is presented through calculations of various structural distributions in different conical shells around the perpendicular axis of the ion. The nitrate ion-water dimer potential energies are also calculated for many different orientations of water. The average vibrational stretch frequency of OD modes in the solvation shell is found to be higher than that of other OD modes in the bulk, which signifies a weakening of hydrogen bonds in the hydration shell. A splitting of the NO stretch frequencies and an associated fast spectral diffusion of the solute are also observed in the current study. The dynamics of rotation and hydrogen bond relaxation are found to be faster in the hydration shell than that in the bulk water. The residence time of water in the hydration shell is, however, found to be rather long. The nitrate ion is found to have a dipole moment of 0.9 D in water which can be attributed to its fluctuating interactions with the surrounding water.

Dynamic nuclear polarization via thermal mixing: Beyond the high temperature approximation

Dynamic Nuclear Polarization (DNP) via the mechanism of thermal mixing has proven itself most powerful for the orientation of nuclear spins in polarized targets and hyperpolarization for magnetic resonance imaging (MRI). Unfortunately, theoretical descriptions of this mechanism have been limited to using—at least partially—the high temperature approximation, in which Boltzmann factors are expanded linearly. However, the high nuclear spin polarization required and obtained for these applications does not justify such approximations.This article extends the description of thermal mixing beyond the high temperature approximation, so Boltzmann factors are not expanded. It applies for DNP in samples doped with paramagnetic centres, for which the electron spin resonance spectrum is mainly inhomogeneously broadened by g-value anisotropy. It verifies Provotorov’s hypothesis that fast spectral diffusion leads to a density matrix containing two inverse spin temperatures: the inverse electron Zeeman temperature and the inverse electron non-Zeeman temperature, while thermal mixing equalizes the nuclear Zeeman temperature and the electron non-Zeeman temperature. Equations are derived for the evolution of these temperatures and the energy flows between the spins and the lattice. Solutions are given for DNP of proton spins in samples doped with the radical TEMPO.

Nuclear spin decoherence of neutralP31donors in silicon: Effect of environmentalSi29nuclei

Spectral diffusion arising from $^{29}$Si nuclear spin flip-flops, known to be a primary source of electron spin decoherence in silicon, is also predicted to limit the coherence times of neutral donor nuclear spins in silicon. Here, the impact of this mechanism on $^{31}$P nuclear spin coherence is measured as a function of $^{29}$Si concentration using X-band pulsed electron nuclear double resonance (ENDOR). The $^{31}$P nuclear spin echo decays show that decoherence is controlled by $^{29}$Si flip-flops resulting in both fast (exponential) and slow (non-exponential) spectral diffusion processes. The decay times span a range from 100 ms in crystals containing 50% $^{29}$Si to 3 s in crystals containing 1% $^{29}$Si. These nuclear spin echo decay times for neutral donors are orders of magnitude longer than those reported for ionized donors in natural silicon. The electron spin of the neutral donors `protects' the donor nuclear spins by suppressing $^{29}$Si flip-flops within a `frozen core', as a result of the detuning of the $^{29}$Si spins caused by their hyperfine coupling to the electron spin.

Influence of the Conjugation Length on the Optical Spectra of Single Ladder-Type (p-Phenylene) Dimers and Polymers

We employ low-temperature single-molecule photoluminescence spectroscopy on a π-conjugated ladder-type (p-phenylene) dimer and the corresponding polymer methyl-substituted ladder-type poly(p-phenylene), MeLPPP, to study the impact of the conjugation length (π-electron delocalization) on their optical properties on a molecular scale. Our data show that the linear electron-phonon coupling to intramolecular vibrational modes is very sensitive to the conjugation length, a well-known behavior of organic (macro-) molecules. In particular, the photoluminescence spectra of single dimers feature a rather strong low-energy (150 cm(-1)) skeletal mode of the backbone, which does not appear in the spectra of individual chromophores on single MeLPPP chains. We attribute this finding to a strongly reduced electron-phonon coupling strength and/or vibrational energy of this mode for MeLPPP with its more delocalized π-electron system as compared to the dimer. In contrast, the line widths of the purely electronic zero-phonon lines (ZPL) in single-molecule spectra do not show differences between the dimer and MeLPPP; for both systems the ZPLs are apparently broadened by fast unresolved spectral diffusion. Finally, we demonstrate that the low-temperature ensemble photoluminescence spectrum of the dimer cannot be reproduced by the distribution of spectral positions of the ZPLs. The dimer's bulk spectrum is rather apparently broadened by electron-phonon coupling to the low-energy skeletal mode, whereas for MeLPPP the inhomogeneous bulk line shape resembles the distribution of spectral positions of the ZPLs of single chromophores.

Center Line Slope Analysis in Two-Dimensional Electronic Spectroscopy.

Center line slope (CLS) analysis in 2D infrared spectroscopy has been extensively used to extract frequency–frequency correlation functions of vibrational transitions. We apply this concept to 2D electronic spectroscopy, where CLS is a measure of electronic gap fluctuations. The two domains, infrared and electronic, possess differences: In the infrared, the frequency fluctuations are classical, often slow and Gaussian. In contrast, electronic spectra are subject to fast spectral diffusion and affected by underdamped vibrational wavepackets in addition to Stokes shift. All these effects result in non-Gaussian peak profiles. Here, we extend CLS-analysis beyond Gaussian line shapes and test the developed methodology on a solvated molecule, zinc phthalocyanine. We find that CLS facilitates the interpretation of 2D electronic spectra by reducing their complexity to one dimension. In this way, CLS provides a highly sensitive measure of model parameters describing electronic–vibrational and electronic–solvent interaction.

Single molecule studies of a ladder type conjugated polymer: vibronic spectra, line widths, and energy transfer.

Confocal fluorescence microscopy and spectroscopy are employed to investigate single poly(ladder-type pentaphenylene) (LPPentP) molecules dispersed in thin poly(methyl methacrylate) (PMMA) films at 1.2 K. Emission spectra of single chains show single as well as multi-chromophore emission indicating variegated communication along the chains. The vibronic structure in the emission spectra resembles the one found for other ladder-type polymers. Purely electronic zero-phonon lines in emission are substantially broadened, most probably due to fast spectral diffusion. By surmounting the limitations of emission spectroscopy, nonemitting donor chromophores, which transfer their excitation energy in a radiationless manner to emitting chromophores, are accessed by excitation spectroscopy. Remarkably, by comparing the data of emitting and nonemitting chromophores a contribution to the zero-phonon excitation line width has to be considered which places a lower limit on the estimated energy transfer time of several picoseconds between adjacent chromophores. Finally, the data indicate qualitatively a restricted flexibility of LPPentP compared to poly[2-methoxy-5-(2'-ethyl-hexyloxy)-1,4-phenylene vinylene] (MEH-PPV).

Dynamics of water, methanol, and ethanol in a room temperature ionic liquid.

The dynamics of a series of small molecule probes with increasing alkyl chain length: water, methanol, and ethanol, diluted to low concentration in the room temperature ionic liquid 1-ethyl-3-methylimidazolium bis(trifluoromethylsulfonyl)imide, was investigated with 2D infrared vibrational echo (2D IR) spectroscopy and polarization resolved pump-probe (PP) experiments on the deuterated hydroxyl (O-D) stretching mode of each of the solutes. The long timescale spectral diffusion observed by 2D IR, capturing complete loss of vibrational frequency correlation through structural fluctuation of the medium, shows a clear but not dramatic slowing as the probe alkyl chain length is increased: 23 ps for water, 28 ps for methanol, and 34 ps for ethanol. Although in each case, only a single population of hydroxyl oscillators contributes to the infrared line shapes, the isotropic pump-probe decays (normally caused by population relaxation) are markedly nonexponential at short times. The early time features correspond to the timescales of the fast spectral diffusion measured with 2D IR. These fast isotropic pump-probe decays are produced by unequal pumping of the OD absorption band to a nonequilibrium frequency dependent population distribution caused by significant non-Condon effects. Orientational correlation functions for these three systems, obtained from pump-probe anisotropy decays, display several periods of restricted angular motion (wobbling-in-a-cone) followed by complete orientational randomization. The cone half-angles, which characterize the angular potential, become larger as the experimental frequency moves to the blue. These results indicate weakening of the angular potential with decreasing hydrogen bond strength. The slowest components of the orientational anisotropy decays are frequency-independent and correspond to the complete orientational randomization of the solute molecule. These components slow appreciably with increasing chain length: 25 ps for water, 42 ps for methanol, and 88 ps for ethanol. The shape and volume of the probe, therefore, impact reorientation far more severely than they do spectral diffusion at long times, though these two processes occur on similar timescales at earlier times.

Origins of Spectral Broadening in Iodated Vaska’s Complex in Binary Solvent Mixtures

Linear absorption spectroscopy of the iridium-bound carbonyl on an iodated adduct of Vaska's complex has shown that the mean vibrational frequency is insensitive to solvation by a broad range of solvents, while the spectral line width changes significantly. The spectral broadening is more significant in chloroform than benzyl alcohol, which is puzzling considering that benzyl alcohol is more polar. In this study, 2D-IR spectroscopy was performed on this vibrational mode to dissect the linear line shape into its homogeneous and inhomogeneous contributions in binary solvent mixtures of either chloroform or benzyl alcohol in d6-benzene. The full frequency-frequency correlation function was determined, including the homogeneous line width and fast spectral diffusion. We find that the frequency fluctuation magnitudes show the most notable changes in chloroform mixtures, while the time constants for spectral diffusion change more dramatically in benzyl alcohol mixtures. Nonetheless, we conclude that the frequency fluctuation magnitudes in both solvent mixtures most clearly explain the differences in their linear line widths. The homogeneous contributions were found to either stay the same or decrease as the more polar solvent was added to d6-benzene, thereby implicating inhomogeneous dynamics as the dominant broadening mechanism.

Extraction of the homogeneous linewidth of the spectrally diffusing line of a CdSe/ZnSe quantum dot embedded in a nanowire

We present a simple method to extract the homogeneous linewidth of a single photon emitter line exhibiting fast (down to 1 ns) spectral diffusion (SD). It is based on a recently developed technique using photon correlation measurements on half of the line. Here we show that the SD induced bunching depends on the ratio between the width of the homogeneous line and the spectral diffusion amplitude. Using this technique on a CdSe/ZnSe quantum dot, we investigate the temperature dependence of its fast SD amplitude and its homogeneous excitonic linewidth

Water Dynamics in Water/DMSO Binary Mixtures

The dynamics of dimethyl sulfoxide (DMSO)/water solutions with a wide range of water concentrations are studied using polarization selective infrared pump-probe experiments, two-dimensional infrared (2D IR) vibrational echo spectroscopy, optical heterodyne detected optical Kerr effect (OHD-OKE) experiments, and IR absorption spectroscopy. Vibrational population relaxation of the OD stretch of dilute HOD in H(2)O displays two vibrational lifetimes even at very low water concentrations that are associated with water-water and water-DMSO hydrogen bonds. The IR absorption spectra also show characteristics of both water-DMSO and water-water hydrogen bonding. Although two populations are observed, water anisotropy decays (orientational relaxation) exhibit single ensemble behavior, indicative of concerted reorientation involving water and DMSO molecules. OHD-OKE experiments, which measure the orientational relaxation of DMSO, reveal that the DMSO orientational relaxation times are the same as orientational relaxation times found for water over a wide range of water concentrations within experimental error. The fact that the reorientation times of water and DMSO are basically the same shows that the reorientation of water is coupled to the reorientation of DMSO itself. These observations are discussed in terms of a jump reorientation model. Frequency-frequency correlation functions determined from the 2D IR experiments on the OD stretch show both fast and slow spectral diffusion. In analogy to bulk water, the fast component is assigned to very local hydrogen bond fluctuations. The slow component, which is similar to the slow water reorientation time at each water concentration, is associated with global hydrogen bond structural randomization.

Quantum Light Signatures and Nanosecond Spectral Diffusion from Cavity-Embedded Carbon Nanotubes

Single-walled carbon nanotubes (SWCNTs) are considered for novel optoelectronic and quantum photonic devices, such as single photon sources, but methods must be developed to enhance the light extraction and spectral purity, while simultaneously preventing multiphoton emission as well as spectral diffusion and blinking in dielectric environments of a cavity. Here we demonstrate that utilization of nonpolar polystyrene as a cavity dielectric completely removes spectral diffusion and blinking in individual SWCNTs on the millisecond to multisecond time scale, despite the presence of surfactants. With these cavity-embedded SWCNT samples, providing a 50-fold enhanced exciton emission into the far field, we have been able to carry out photophysical studies for the first time with nanosecond timing resolution. We uncovered that fast spectral diffusion processes (1-3 ns) remain that make significant contributions to the spectral purity, thereby limiting the use of SWCNTs in quantum optical applications requiring indistinguishable photons. Measured quantum light signatures reveal pronounced photon antibunching (g(2)(0) = 0.15) accompanied by side-peak bunching signatures indicative of residual blinking on the submicrosecond time scale. The demonstrated enhanced single photon emission from cavity-embedded SWCNTs is promising for applications in quantum key distribution, while the demonstrated passivation effect of polystyrene with respect to the stability of the optical emission opens a novel pathway toward optoelectronic devices with enhanced performance.

Spectral diffusion at the water/lipid interface revealed by two-dimensional fourth-order optical spectroscopy: a classical simulation study.

Using a classical simulation protocol for nonlinear optical signals, we predict the two-dimensional (2D) spectra of water near a monolayer of [1,2-dimytristoyl-sn-glycero-3-phosphatidylcholine] (DMPC) generated by three IR probe pulses followed by one visible probe pulse. Sum-frequency-generation 1D spectra show two peaks of the OH stretch representing two environments: near-bulk water nonadjacent to DMPC and top-layer water adjacent to DMPC. These peaks create a 2D pattern in the fourth-order signal. The asymmetric cross-peak pattern with respect to the diagonal line is a signature of coherence transfer from the higher- to the lower-frequency modes. The nodal lines in the imaginary part of the 2D spectrum show that the near-bulk water has fast spectral diffusion resembling that of bulk water despite the orientation by the strong electrostatic field of DMPC. The top-layer water has slower spectral diffusion.

Modeling coherence measurements on a spectrally diffusing single-photon emitter

We examine the possibility of measuring the emission linewidth $2\ensuremath{\hbar}{\ensuremath{\Gamma}}_{2}$ of a single-photon source by Michelson interferometry. Such an emitter is characterized by a limited fluorescence intensity and, when embedded in a solid matrix, a large spectral diffusion. We show that fast spectral diffusion renders standard Fourier spectroscopy irrelevant. We then calculate the correlations of the intensities detected at the two interferometer outputs, point out the existence of two-photon interferences (coalescence) even for a non-single-mode emission, and show that the correlations are not affected by spectral diffusion at correlation times shorter than spectral dynamics. This yields two ways to measure the decoherence rate ${\ensuremath{\Gamma}}_{2}$: the recently proposed photon-correlation Fourier spectroscopy, and the study of the coalescence dip. We examine the feasibility and spectral resolution of each method, depending on spectral-diffusion characteristics, and show that both methods could be applied to typical nanometer-sized emitters such as colloidal quantum dots.

Multidimensional infrared spectroscopy of a peptide intramolecular hydrogen bond

Stimulated three pulse photon echoes and heterodyned 2D IR echoes of acetylproline-NHMe in CHCl 3 are reported. A global fitting of the pump/probe decays of the internally hydrogen bonded N–H stretching vibration of AcProNHMe in CHCl 3 gives two population relaxation times of 400 and 1300 fs, which suggest the existence of different hydrogen bonded structures. Two different responses are clearly demonstrated in the 2D spectra, | S ∼ ( τ , T , ω t ) | ; one of them appears to be a more homogeneous response than the other. This function peaks at τ-values which decrease with a sub-100 fs time constant to a plateau of ca. τ = 70 fs. This decay implies fast spectral diffusion and the persistent non-zero offset suggests that a large static inhomogeneity exists in the whole time range considered in this experiment, which implies the existence of a rigid hydrogen bonded structure on the time scale of many picoseconds. The spectral shape of the 2D IR could not be reproduced by conventional responses for independent oscillators having overlapping transitions. It is suggested that the two hydrogen bond configurations are exchanging rapidly and the shape of the 2D IR spectra is determined by the two chemically interchanging structures. In this paper multidimensional IR spectroscopy clearly shows the potential to disentangle congested spectra by spreading them into two dimensions and expose multiple structures, which are not seen distinctly in the FTIR spectra. The correlation function of the H-bonded N–H group is dominated by a ca. 100 fs component that is suggested to represent overdamped internal structure fluctuations.

Non-photochemical spectral hole-burning mediated by water molecules in interligand pockets of [Cr(terpy)2]3+

Low temperature fluorescence line-narrowing (FLN) and spectral hole-burning experiments (SHB) were performed in the 2E←4A2 spin–flip transition of [Cr(2,2′:6′,2″-terpyridine)2]3+ in frozen ethylene glycol/water (2 ∶ 1) and DMSO/water (2 ∶ 1) glasses. In the FLN experiments an average 2E splitting of 23 cm−1 is observed. It is concluded that the interaction with water molecules in pockets provided by the ligands is most likely to be responsible for the relatively efficient non-photochemical hole-burning. Fast spectral diffusion and spontaneous hole-filling prevent the observation of holes above 20 K. The FLN and SHB experiments were performed by using a diode laser.