Femtosecond Spectroscopy Research Articles

Femtosecond Spectroscopy on a Dibenzophenazine-Cored Macrocycle Exhibiting Thermally Activated Delayed Fluorescence.

The photophysics of a thermally activated delayed fluorescence (TADF) emitting macrocycle consisting of two dibenzo[a,j]phenazine acceptor moieties bridged by two N,N,N',N'-tetraphenylene-1,4-diamine donor units was scrutinized in solution by steady-state and time-resolved spectroscopy. The fluorescence lifetime of the compound proved to be strongly solvent-dependent. It ranges from 6.3 ns in cyclohexane to 34 ps in dimethyl sulfoxide. In polar solvents the fluorescence decay is predominantly due to internal conversion. In non-polar ones radiative decay and intersystem crossing contribute. Contrary to the behaviour in polymer matrices (S. Izumi et al., J. Am. Chem. Soc. 2020, 142, 1482) the excited state decay is not predominantly due to prompt and delayed fluorescence. The solvent-dependent behaviour is analyzed with the aid of quantum chemical computations.

Exploring the Microscopic Aspects of 1-Methyl-3-octylimidazolium Tetrafluoroborate Mixtures with Formamide, N-Methylformamide, and N,N-Dimethylformamide by Multiple Spectroscopic Techniques and Computations.

The microscopic aspects of 1-methyl-3-octylimidazolium tetrafluoroborate ([MOIm][BF4]) mixtures with formamide (FA), N-methylformamide (NMF), and N,N-dimethylformamide (DMF) were investigated using spectroscopic techniques of femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES), FT-IR, and NMR. Molecular dynamics simulations and quantum chemistry calculations were also performed. According to fs-RIKES, the first moment of the low-frequency spectrum bands mainly originating from the intermolecular vibrations in the [MOIm][BF4]/FA and [MOIm][BF4]/DMF systems changed gradually with the molecular liquid mole fraction XML but that in the [MOIm][BF4]/NMF system was constant up to XNMF = 0.7 and then gradually increased in the range of XNMF ≥ 0.7. Excluding the contribution of the 2D hydrogen-bonding network due to the presence of FA in the low-frequency spectrum band, the XML dependence of the normalized first moment of the low-frequency band in the [MOIm][BF4]/FA and [MOIm][BF4]/NMF systems revealed that the normalized first moment did not remarkably change in the range of XML < 0.7 but drastically increased in XML ≥ 0.7. FT-IR results indicated that the amide C═O band shifted to the low-frequency side with increasing XML for the three mixtures due to the hydrogen bonds. The imidazolium ring C-H band also showed a similar tendency to the amide C═O band. 19F NMR probed the microenvironment of [BF4]- in the mixtures. The [MOIm][BF4]/NMF and [MOIm][BF4]/DMF systems showed an up-field shift of the F atoms of the anion with increasing XML, and the [MOIm][BF4]/FA system exhibited a down-field shift. Steep changes in the chemical shifts were confirmed in the region of XML > 0.8. On the basis of the quantum chemistry calculations, the observed chemical shifts with increasing XML were mainly attributed to the many-body interactions of ions and amides for the [MOIm][BF4]/FA and [MOIm][BF4]/DMF systems. Meanwhile, the long distance between the cation and the anion was due to the high dielectric medium for the [MOIm][BF4]/NMF system, which led to an up-field shift.

Inverted region in the reaction of the quinone reduction in the A1-site of photosystem I from cyanobacteria.

Photosystem I from the menB strain of Synechocystis sp. PCC 6803 containing foreign quinones in the A1 sites was used for studying the primary steps of electron transfer by pump-probe femtosecond laser spectroscopy. The free energy gap (- ΔG) of electron transfer between the reduced primary acceptor A0 and the quinones bound in the A1 site varied from 0.12eV for the low-potential 1,2-diamino-anthraquinone to 0.88eV for the high-potential 2,3-dichloro-1,4-naphthoquinone, compared to 0.5eV for the native phylloquinone. It was shown that the kinetics of charge separation between the special pair chlorophyll P700 and the primary acceptor A0 was not affected by quinone substitutions, whereas the rate of A0 → A1 electron transfer was sensitive to the redox-potential of quinones: the decrease of - ΔG by 400meV compared to the native phylloquinone resulted in a ~ fivefold slowing of the reaction The presence of the asymmetric inverted region in the ΔG dependence of the reaction rate indicates that the electron transfer in photosystem I is controlled by nuclear tunneling and should be treated in terms of quantum electron-phonon interactions. A three-mode implementation of the multiphonon model, which includes modes around 240cm-1 (large-scale protein vibrations), 930cm-1 (out-of-plane bending of macrocycles and protein backbone vibrations), and 1600cm-1 (double bonds vibrations) was applied to rationalize the observed dependence. The modes with a frequency of at least 1600cm-1 make the predominant contribution to the reorganization energy, while the contribution of the "classical" low-frequency modes is only 4%.

Aggregation-Induced Stimulated Emission of 100% Dye Microspheres.

Dyes with aggregation-induced emission (AIE) properties have gained interests due to their bright luminescence in solid-state aggregates. While fluorescence from AIE dyes have been widely exploited, relatively little is known about aggregation-induced stimulated emission. Here, we investigated stimulated emission of tetraphenylethene (TPE)-based organoboron AIE dyes, TPEQBN, in thin films and in microcavity lasers. Using femtosecond pump-probe spectroscopy, gain coefficients up to 230 cm-1 at 500 nm were measured. Using rate equations, we analyzed concentration- and pump-dependent gain dynamics as well as laser build up dynamics. During laser oscillation, radiative stimulated emission allows high instantaneous quantum yield greater than 90% to be achieved. We fabricated solid-state microspheres made of 100% AIE dyes via microfluidic emulsion and solvent evaporation method. Coupled with high gain and high refractive index of 1.76, microspheres as small as 2 μm in diameter showed lasing by nanosecond pumping with a threshold of ~10 pJ μm-2. Polymer coated, but not bare, microspheres were internalized by live cells and generated narrowband cavity mode emission from within the cytoplasm. Our work shows the potential of AIE dyes as laser materials.

Peptide Bond of Aqueous Dipeptides Is Resilient to Deep Ultraviolet Irradiation

The susceptibility of aqueous dipeptides to photodissociation by deep ultraviolet irradiation is studied by femtosecond spectroscopy supported by density functional theory calculations. The primary photodynamics of the aqueous dipeptides of glycyl-glycine (gly-gly), alalyl-alanine (ala-ala), and glycyl-alanine (gly-ala) show that upon photoexcitation at a wavelength of 200 nm, about 10% of the excited dipeptides dissociate by decarboxylation within 100 ps, while the rest of the dipeptides return to their native ground state. Accordingly, the vast majority of the excited dipeptides withstand the deep ultraviolet excitation. In those relatively few cases, where excitation leads to dissociation, the measurements show that deep ultraviolet irradiation breaks the Cα-C bond rather than the peptide bond. The peptide bond is thereby left intact, and the decarboxylated dipeptide moiety is open to subsequent reactions. The experiments indicate that the low photodissociation yield and in particular the resilience of the peptide bond to dissociation are due to rapid internal conversion from the excited state to the ground state, followed by efficient vibrational relaxation facilitated by intramolecular coupling among the carbonate and amide modes. Thus, the entire process of internal conversion and vibrational relaxation to thermal equilibrium on the dipeptide ground state occurs on a time scale of less than 2 ps.

Hot Carrier Cooling and Trapping in Atomically Thin WS2 Probed by Three-Pulse Femtosecond Spectroscopy

Transition metal dichalcogenides (TMDs) have shown outstanding semiconducting properties which make them promising materials for next-generation optoelectronic and electronic devices. These properties are imparted by fundamental carrier-carrier and carrier-phonon interactions that are foundational to hot carrier cooling. Recent transient absorption studies have reported ultrafast time scales for carrier cooling in TMDs that can be slowed at high excitation densities via a hot-phonon bottleneck (HPB) and discussed these findings in the light of optoelectronic applications. However, quantitative descriptions of the HPB in TMDs, including details of the electron-lattice coupling and how cooling is affected by the redistribution of energy between carriers, are still lacking. Here, we use femtosecond pump-push-probe spectroscopy as a single approach to systematically characterize the scattering of hot carriers with optical phonons, cold carriers, and defects in a benchmark TMD monolayer of polycrystalline WS2. By controlling the interband pump and intraband push excitations, we observe, in real-time (i) an extremely rapid "intrinsic" cooling rate of ∼18 ± 2.7 eV/ps, which can be slowed with increasing hot carrier density, (ii) the deprecation of this HPB at elevated cold carrier densities, exposing a previously undisclosed role of the carrier-carrier interactions in mediating cooling, and (iii) the interception of high energy hot carriers on the subpicosecond time scale by lattice defects, which may account for the lower photoluminescence yield of TMDs when excited above band gap.

Discrimination of tooth composition through temporally shaped femtosecond laser-induced breakdown spectroscopy

Dental caries has attracted widespread concern because of its universality. However, the current diagnosis of dental caries depends largely on naked eyes and dentists' experience, which causes considerable randomness and inaccuracy in the diagnosis. In this study, temporally shaped double pulse (DP) femtosecond laser-induced breakdown spectroscopy (LIBS) has been used for tooth composition detection for the first time. Under the laser fluence of 20 J/cm2, the spectra intensity for DP LIBS with a pulse delay of 200 ps was 13 times higher than that of single pulse. For further prediction, the detection model based on DP LIBS and partial least squares discrimination analysis could discriminate dentin, enamel, and caries with a prediction accuracy of above 90%. This method may provide rapid and accurate feedback to dentists for real-time diagnosis in the future.

Ultrafast Heat Transfer at the Nanoscale: Controlling Heat Anisotropy

Thermoplasmonics has benefited from increasing attention in recent years by exploiting the photothermal effects within plasmonic nanoparticles to generate nanoscale heat sources. Recently, it has been demonstrated that exciting gold nanoparticles with ultrashort light pulses could be used to achieve high-speed light management and nanoscale heat-sensitive chemical reaction control. In this work, we study non-uniform thermal energy transient distribution inside cross-shaped nanostructures with femtosecond transient spectroscopy coupled to a thermo-optical numerical model, free of fitting parameters. We show experimentally and numerically that the polarization of the excitation light can control the heat distribution in the nanostructures. We also demonstrate the necessity of considering nonthermal electron ballistic displacement in fast transient heat dynamics models.

Ground-state heterogeneity and vibrational energy redistribution in bacterial phytochrome observed with femtosecond 2D IR spectroscopy.

Phytochromes belong to a group of photoreceptor proteins containing a covalently bound biliverdin chromophore that inter-converts between two isomeric forms upon photoexcitation. The existence and stability of the photocycle products are largely determined by the protein sequence and the presence of conserved hydrogen-bonding interactions in the vicinity of the chromophore. The vibrational signatures of biliverdin, however, are often weak and obscured under more intense protein bands, limiting spectroscopic studies of its non-transient signals. In this study, we apply isotope-labeling techniques to isolate the vibrational bands from the protein-bound chromophore of the bacterial phytochrome from Deinococcus radiodurans. We elucidate the structure and ultrafast dynamics of the chromophore with 2D infra-red (IR) spectroscopy and molecular dynamics simulations. The carbonyl stretch vibrations of the pyrrole rings show the heterogeneous distribution of hydrogen-bonding structures, which exhibit distinct ultrafast relaxation dynamics. Moreover, we resolve a previously undetected 1678cm-1 band that is strongly coupled to the A- and D-ring of biliverdin and demonstrate the presence of complex vibrational redistribution pathways between the biliverdin modes with relaxation-assisted measurements of 2D IR cross peaks. In summary, we expect 2D IR spectroscopy to be useful in explaining how point mutations in the protein sequence affect the hydrogen-bonding structure around the chromophore and consequently its ability to photoisomerize to the light-activated states.

Measuring Photoexcited Electron and Hole Dynamics in ZnTe and Modeling Excited State Core-Valence Effects in Transient Extreme Ultraviolet Reflection Spectroscopy

Transient extreme ultraviolet (XUV) spectroscopy is becoming a valuable tool for characterizing solar energy materials because it can separate photoexcited electron and hole dynamics with element specificity. Here, we use surface-sensitive femtosecond XUV reflection spectroscopy to separately measure photoexcited electron, hole, and band gap dynamics of ZnTe, a promising photocathode for CO2 reduction. We develop an ab initio theoretical framework based on density functional theory and the Bethe-Salpeter equation to robustly assign the complex transient XUV spectra to the material's electronic states. Applying this framework, we identify the relaxation pathways and quantify their time scales in photoexcited ZnTe, including subpicosecond hot electron and hole thermalization, surface carrier diffusion, ultrafast band gap renormalization, and evidence of acoustic phonon oscillations.

Photoionization of 3-Methylindole Embedded in Sodium Dodecyl Sulfate and Dodecyltrimethylammonium Chloride Micelles: Migration of Electrons Generated in Micelle Cores and Their Solvation in Outside Water

Electrons were generated in the core of micelles formed by negatively charged sodium dodecyl sulfate (SDS) or positively charged dodecyltrimethylammonium chloride (DTAC) by photoionization of 3-methylindole embedded in the core. The electrons were hydrated after they moved out of the core to the outer aqueous phase. These processes were monitored with femtosecond time-resolved absorption spectroscopy. The migration of electrons from the micelle core to the outer aqueous phase was faster than the instrumental response time of 200 fs. Hot electrons in the aqueous phase were produced in ≤320 fs. There was no significant difference observed for the micellar solutions of negatively charged SDS and positively charged DTAC, or for water. The geminate recombination between the electrons and the radical cations was hindered to a large extent once the electrons hydrated at the outer aqueous phase were separated from the radical cations remaining in the micelle core.

Photochemical Processes of Superbase Generation in Xanthone Carboxylic Salts

AbstractPhotobase generators are species that allow the photocatalysis of various reactions, such as thiol‐Michael, thiol‐isocyanate, and ring‐opening polymerization reactions. However, existing compounds have complex syntheses and low quantum yields. To overcome these problems, photobase generators based on the photodecarboxylation reaction were developed. We synthesized and studied the photochemistry and photophysics of two xanthone photobase, their carboxylic acid precursors, and their photoproducts to understand the photobase generation mechanism. We determined accurate quantum yields of triplet states and photobase generation. The effect of the intermediate radical preceding the base release was demonstrated. We characterized the photophysics of the photobase by femtosecond spectroscopy and showed that the photodecarboxylation process occurred from the second excited triplet state with a rate constant of 2.2×109 s−1.

Photochemical Processes of Superbase Generation in Xanthone Carboxylic Salts.

Photobase generators are species that allow the photocatalysis of various reactions, such as thiol-Michael, thiol-isocyanate, and ring-opening polymerization reactions. However, existing compounds have complex syntheses and low quantum yields. To overcome these problems, photobase generators based on the photodecarboxylation reaction were developed. We synthesized and studied the photochemistry and photophysics of two xanthone photobase, their carboxylic acid precursors, and their photoproducts to understand the photobase generation mechanism. We determined accurate quantum yields of triplet states and photobase generation. The effect of the intermediate radical preceding the base release was demonstrated. We characterized the photophysics of the photobase by femtosecond spectroscopy and showed that the photodecarboxylation process occurred from the second excited triplet state with a rate constant of 2.2×109 s-1 .

Observing Nonpreferential Absorption of Linear and Cyclic Carbonate on the Silicon Electrode.

Silicon is reported to be a promising anode material due to its high storage capacity and excellent energy conversion rate. Molecular-level insight into the interaction between silicon electrodes and electrolyte solutions is essential for understanding the formation of a stable solid electrolyte interphase (SEI), but it is yet to be explored. In this study, we apply femtosecond sum frequency generation vibrational spectroscopy to investigate the initial adsorption of various pure and mixed electrolyte molecules on the silicon anode surface by monitoring the SFG signals from the carbonyl group of electrolyte molecules. When the silicon comes in contact with a pure carbonate solution, the linear carbonates of diethyl carbonate and ethyl methyl carbonate adopt two conformations with opposite C═O orientations on the silicon interface while the cyclic carbonates of ethylene carbonate and propylene carbonate almost adopt one conformation with C═O bonds pointing toward the silicon electrode. When the silicon comes in contact with the mixed linear and cyclic carbonate solutions, the total SFG intensity from the mixed solutions is approximately 2∼5 times weaker than those of pure cyclic carbonates. The C═O bonds of cyclic carbonates point toward the silicon electrode, while the C═O bonds of linear carbonates face toward the bulk solution at the silicon/mixed solution interface. No preferential absorption behaviors of the linear and cyclic carbonate electrolytes on the silicon electrode are observed. Such findings may help to understand the mechanism by which the SEI formed on the silicon anode is unstable.

Present State of Knowledge of Chemistry of Our Vision: Photoreceptor Molecules and Vision Cycle

Vision process involves the participation of two types of retinal photoreceptor cells: rod cells respond to dim light while cone cells respond to bright light and colours. The visual pigments in both types of photoreceptor cells contain the common chromophore, 11-cis-retinal, linked through a Schiff base linkage to the opsin protein, a member of G-protein coupled receptor (GPCR) family, composed of 7-transmembrane helices (a 7TM receptor). Rhodopsin is the visual pigment present in the rod cells while three distinct types of visual pigments known as photopsins (red cones, green cones and blue cones absorbing red, blue and green parts of the visible spectrum respectively) are present in the cone cells. Absorption of light by the visual pigment causes the photoexcitation followed by photoisomerization, 11-cis-retinal (Z) to all-trans-retinal (E) with a high quantum yield through a number of reactive intermediates characterized by low temperature and picosecond (ps) time resolved spectroscopies coupled with femtosecond spectroscopy. This photoisomerization leads to a change in the conformation of opsin GPCR and a signal transduction cascade by activating transducin, a heterotrimeric G-protein, to breakdown the cGMP to close the cGMP-gated cation channels resulting in hyperpolarization of the photoreceptor cell. This action potential creates a nerve signal that is transmitted to the brain to produce the sense of vision. The photoisomerized pigment undergoes rapidly hydrolysis to produce the opsin protein and all trans-retinal, which can be reconverted enzymatically to 11-cis-retinal for recharging opsin to generate the active visual pigment to maintain the vision cycle (Wald cycle). This brief review highlights the state of our understanding of the biology behind the art of vision in humans and other organisms.

Intense femtosecond optical pulse shaping approaches to spatiotemporal control.

For studying any event, measurement can never be enough; "control" is required. This means mere passive tracking of the event is insufficient and being able to manipulate it is necessary. To maximize this capability to exert control and manipulate, both spatial and temporal domains need to be jointly accounted for, which has remained an intractable problem at microscopic scales. Simultaneous control of dynamics and position of an observable event requires a holistic combination of spatial and temporal control principles, which gives rise to the field of spatiotemporal control. For this, we present a novel femtosecond pulse-shaping approach. We explain how to achieve spatiotemporal control by spatially manipulating the system through trapping and subsequently or simultaneously exerting temporal control using shaped femtosecond pulses. By leveraging ultrafast femtosecond lasers, the prospect of having temporal control of molecular dynamics increases, and it becomes possible to circumvent the relaxation processes at microscopic timescales. Optical trapping is an exemplary demonstration of spatial control that results in the immobilization of microscopic objects with radiation pressure from a tightly focused laser beam. Conventional single-beam optical tweezers use continuous-wave (CW) lasers for achieving spatial control through photon fluxes, but these lack temporal control knobs. We use a femtosecond high repetition rate (HRR) pulsed laser to bypass this lack of dynamical control in the time domain for optical trapping studies. From a technological viewpoint, the high photon flux requirement of stable optical tweezers necessitates femtosecond pulse shaping at HRR, which has been a barrier until the recent Megahertz pulse shaping developments. Finally, recognizing the theoretical distinction between tweezers with femtosecond pulses and CW lasers is of paramount interest. Non-linear optical (NLO) interactions must be included prima facie to understand pulsed laser tweezers in areas where they excel, like the two-photon-fluorescence-based detection. We show that our theoretical model can holistically address the common drawback of all tweezers. We are able to mitigate the effects of laser-induced heating by balancing this with femtosecond laser-induced NLO effects. An interesting side-product of HRR femtosecond-laser-induced thermal lens is the development of femtosecond thermal lens spectroscopy (FTLS) and its ability to provide sensitive molecular detection.

Physical Properties and Low-Frequency Polarizability Anisotropy and Dipole Responses of Phosphonium Bis(fluorosulfonyl)amide Ionic Liquids with Pentyl, Ethoxyethyl, or 2-(Ethylthio)ethyl Group

This study compared the physical properties, e.g., glass transition temperature, melting point, viscosity, density, surface tension, and electrical conductivity, and the low-frequency spectra under 200 cm-1 of three synthesized ionic liquids (ILs), triethylpentylphosphonium bis(fluorosulfonyl)amide ([P2225][NF2]), ethoxyethyltriethylphosphonium bis(fluorosulfonyl)amide ([P222(2O2)][NF2]), and triethyl[2-(ethylthio)ethyl]phosphonium bis(fluorosulfonyl)amide ([P222(2S2)][NF2]), at various temperatures using femtosecond Raman-induced Kerr effect spectroscopy (fs-RIKES) and terahertz time-domain spectroscopy (THz-TDS). The [P222(2S2)][NF2] had the highest viscosity and glass transition temperature, whereas the [P222(2O2)][NF2] had the lowest. Among the three ILs, the [P222(2S2)][NF2] had the highest density and surface tension, and the [P222(2O2)][NF2] had the highest electrical conductivity. The RIKES and THz-TDS spectral line shapes for the three ILs varied significantly. For the [P2225][NF2], molecular dynamics simulations successfully reproduced the line shapes of the experimental spectra and indicated that the RIKES spectrum was mainly due to the cation and cross-term and their rotational motions, whereas the THz-TDS spectrum was mainly due to the anion and its translational motion. This shows that it is desirable to utilize both fs-RIKES and THz-TDS methods to reveal molecular motions at the low-frequency domain. The [P222(2S2)][NF2] had higher frequency peaks and broader bands in the low-frequency spectra via fs-RIKES and THz-TDS than those for the [P2225][NF2] and [P222(2O2)][NF2].

The effect of the duration of laser pulses on the spectral-temporal characteristics of laser plasma in femtosecond laser-induced breakdown spectroscopy of human hair

The effect of the duration of laser pulses of 40 and 650 fs with an energy of 1.1 mJ at a wavelength of 800 nm on the spectral-temporal characteristics of plasma during femtosecond laser-induced breakdown spectroscopy of human hair has been studied. The time dependences of the radiation line intensities of Ca I 422.6 nm, C I 193.1 nm, C I 247.8 nm, Ca II 396.8 nm, Mg II 279.5 nm, Zn II 206.2 nm and the continuous plasma spectrum in the range from 0 to 1 μs are obtained Keywords: emission spectrum, laser plasma, human hair.

Present State of Knowledge of Chemistry of Our Vision: Photoreceptor Molecules and Vision Cycle

Vision process involves the participation of two types of retinal photoreceptor cells: rod cells respond to dim light while cone cells respond to bright light and colours. The visual pigments in both types of photoreceptor cells contain the common chromophore, 11-cis-retinal, linked through a Schiff base linkage to the opsin protein, a member of G-protein coupled receptor (GPCR) family, composed of 7- transmembrane helices (a 7TM receptor). Rhodopsin is the visual pigment present in the rod cells while three distinct types of visual pigments known as photopsins (red cones, green cones and blue cones absorbing red, blue and green parts of the visible spectrum respectively) are present in the cone cells. Absorption of light by the visual pigment causes the photoexcitation followed by photoisomerization, 11-cis-retinal (Z) to all-trans-retinal (E) with a high quantum yield through a number of reactive intermediates characterized by low temperature and picosecond (ps) time resolved spectroscopies coupled with femtosecond spectroscopy. This photoisomerization leads to a change in the conformation of opsin GPCR and a signal transduction cascade by activating transducin, a heterotrimeric G-protein, to breakdown the cGMP to close the cGMP-gated cation channels resulting in hyperpolarization of the photoreceptor cell. This action potential creates a nerve signal that is transmitted to the brain to produce the sense of vision. The photoisomerized pigment undergoes rapidly hydrolysis to produce the opsin protein and all trans-retinal, which can be reconverted enzymatically to 11-cis-retinal for recharging opsin to generate the active visual pigment to maintain the vision cycle (Wald cycle). This brief review highlights the state of our understanding of the biology behind the art of vision in humans and other organisms.

Lattice disorder influences the photocarrier dynamics in lead halide perovskites.

Revealing the structural impact of lead halide perovskites on photocarrier dynamics is essential for the associated solar cells but deficient in experimental visualization. In this study, with femtosecond spectroscopy, we for the first time explored the contribution of the disorder of the distorted PbX6 octahedrons and A-site cations on the carrier behaviours. It was found that photoinduced carriers recombine almost twice slower and diffuse 20% faster in the disordered, β-phased samples than in the ordered, γ-phased ones. Yet within the same phase, with a similar PbX6 orientation but various A-site mobility, the carrier diffusion and recombination have no apparent difference. Thus we firmly conclude that lattice disorder effectively influences the carrier dynamics and therein the Pb-X sublattice is worth more than A-site cations, which should inspire future lead halide perovskite design and applications.