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External pressure is one of the key parameters to understand photoemission nanomaterials since the external pressure changes their photoproperties without introducing any chemical treatment. Here, we computationally elucidated the effects of the external pressure on structures, orbitals, photoproperties, and vibrational dynamics of a silicon vacancy (SiV) diamond nanoslab. We studied its attributes not only on the ground state at 0 K but also on the excited state around room temperature (RT) using an ab initio molecular dynamics simulation. We directly and mechanically pressed the SiV diamond nanoslab fluctuating around RT to mimic an actual external pressure usually generated in an anvil cell at RT. We found that the compression induces the shrunk SiV defect structures, the rearranged defect orbital energies, the switch of the optical transition from the SiV–SiV excitation to the nanoslab–SiV excitation, the hybridization of the SiV with nanoslab carbon (C) orbitals, and the blue shift and the smaller intensity of the spectra of the Si atom oscillation and the inner C–C bond vibration. The energies of absorption, emission, and zero-phonon line do not change monotonically but have the maxima below a 7%-compression. Especially, the absorption energy differs more between 0 K and RT as the compression increases, while the largest deviation between 0 K and RT in the emission energy appears below the 7%-compression. It is remarkable that all of these changes are caused only by the mechanical compression and that the compression differently pronounces the temperature effect. The obtained insights will provide a way to effectively control a split-vacancy center to be a promising single-photon source for nanoscale optical measurements of temperature and pressure in a compressed nanoscale material.

A non-equilibrium molecular flow through a carbon nanotube (CNT) serves as a key system for revealing molecular transport and establishing nanofluidics. It has been challenging to simulate a non-equilibrium flow of hydrogen molecules exhibiting strong nuclear quantumness. Taking advantage of the quantum molecular dynamics method that can calculate real-time trajectories of hydrogen molecules even under a non-equilibrium flow, we found that the non-equilibrium flow makes hydrogen molecules more condensed and accelerates their adsorption near a CNT surface, letting the molecules flow more smoothly by propagating velocity momenta more efficiently along the CNT axis and by suppressing transverse molecular dynamics on the CNT cross section. Such flow-induced autonomic ordering indicates the importance of monitoring and investigating dynamics and adsorption of hydrogen molecules under a non-equilibrium circumstance as well as in a quiet equilibrium state, opening a new strategy for efficient hydrogen liquefaction and storage.

Organic-inorganic nanohybrids using semiconductor nanocrystals (NCs) coordinated with aromatic organic molecules have been widely studied in the fields of optoelectronic materials, such as solar cells, photocatalysis, and photon upconversion. In these materials, coordination bonds of ligand molecules are usually assumed to be stable during optical processes. However, this assumption is not always valid. In this study, we demonstrate that the coordination bonds between ligand molecules and NCs by carboxyl groups are displaced quasi-reversibly by light irradiation using zinc sulfide (ZnS) NCs coordinated with perylenebisimide (PBI) as a model system. Ultrafast spectroscopy and density functional theory calculations show that the photoinduced ligand displacement is driven by ultrafast hole transfer from PBI to ZnS NCs, and that the dissociated radical anion of PBI survives over the second timescale. This study opens up a new avenue for advanced photofunctional materials utilizing colloidal NCs, such as photocatalysts that can expose their active facets of NCs on demand, and sub-micropatterning of photoconductive circuits on solid-state NC films.

Summary Investigating the separate dynamics of electrons and holes has been challenging, although it is critical for the fundamental understanding of semiconducting nanomaterials. n-Type self-doped colloidal quantum dots (CQDs) with excess electrons occupying the low-lying state in the conduction band (CB) have attracted a great deal of attention because of not only their potential applications to infrared optoelectronics but also their intrinsic system that offers a platform for investigating electron dynamics without elusive contributions from holes in the valence band. Here, we show an unprecedented ultrafast intraband Auger process, electron relaxation between spin-orbit coupling states, and exciton-to-ligand vibrational energy transfer process that all occur exclusively in the CB of the self-doped β-HgS CQDs. The electron dynamics obtained by femtosecond mid-infrared spectroscopy will pave the way for further understanding of the blinking phenomenon, disproportionate charging in light-emitting diodes, and hot electron dynamics in higher quantum states coupled to surface states of CQDs.

The success and continued expansion of research on metal-oxo clusters owe largely to their structural richness and wide range of functions. However, while most of them known to date are negatively charged polyoxometalates, there is only a handful of cationic ones, much less functional ones. Here, we show an all-inorganic hydroxyiodide [H₁₀.₇Sb₃₂.₁O₄₄][H₂.₁Sb₂.₁I₈O₆][Sb₀.₇₆I₆]₂·25H₂O (HSbOI), forming a face-centered cubic structure with cationic Sb₃₂O₄₄ clusters and two types of anionic clusters in its interstitial spaces. Although it is submicrometer in size, electron diffraction tomography of HSbOI allowed the construction of the initial structural model, followed by powder Rietveld refinement to reach the final structure. The cationic cluster is characterized by the presence of acidic protons on its surface due to substantial Sb3+ deficiencies, which enables HSbOI to serve as an excellent solid acid catalyst. These results open up a frontier for the exploration and functionalization of cationic metal-oxo clusters containing heavy main group elements., 正電荷の酸化物クラスターの発見 酸触媒としての高い可能性. 京都大学プレスリリース. 2022-06-18., Scientists serendipitously discover rare cluster compound. 京都大学プレスリリース. 2022-06-18.

Understanding how a supercritical fluid is related to normal liquid and gas and separating it into liquid-like and gas-like regions are of fundamental and practical importance. Despite the usefulness of hydrogen storage, molecular dynamics images on supercritical hydrogens exhibiting strong nuclear quantum effects are scarce. Taking advantage of the non-empirical ab initio molecular dynamics method for hydrogen molecules, we found that, while radial distribution functions and diffusion show a monotonic change along the density, van Hove time correlation functions and intramolecular properties such as bond length and vibrational frequency exhibit the anomalous order crossing the Widom line. By demonstrating that the anomalous order stemmed from the largest deviations between liquid-like and gas-like solvations formed around the Widom line, we concluded that this supercritical fluid is a mixture of liquid and gas possessing heterogeneity. The obtained physical insights can be an index to monitor the supercriticality and to identify distinct liquid-like and gas-like supercritical fluids.

Isotopic mixtures of p-H₂ and o-D₂ molecules have been an attractive binary system because they include two kinds of purely isotopic molecules which possess the same electronic potential but the twice different mass inducing differently pronounced nuclear quantum effects (NQEs). Accessing details of structures and dynamics in such quantum mixtures combining complex molecular dynamics with NQEs of different strengths remains a challenging problem. Taking advantage of the nonempirical molecular dynamics method which describes p-H₂ and o-D₂ molecules, we found that the liquid dynamics slows down at a specific mixing ratio, which can be connected to the observed anomalous slowdown of crystallization in the quantum mixtures. We attributed the decelerated dynamics to the component-dependent supercooling of p-H₂ taking place in the mixtures, demonstrating that there is an optimal mixing ratio to hinder crystallization. The obtained physical insights will help in experimentally controlling and achieving unknown quantum mixtures including superfluid.

The conversion of a high-energy photon into two excitons using singlet fission (SF) has stimulated a variety of studies in fields from fundamental physics to device applications. However, efficient SF has only been achieved in limited systems, such as solid crystals and covalent dimers. Here, we established a novel system by assembling 4-(6,13-bis(2-(triisopropylsilyl)ethynyl)pentacen-2-yl)benzoic acid (Pc) chromophores on nanosized CdTe quantum dots (QDs). A near-unity SF (198 ± 5.7%) initiated by interfacial resonant energy transfer from CdTe to surface Pc was obtained. The unique arrangement of Pc determined by the surface atomic configuration of QDs is the key factor realizing unity SF. The triplet-triplet annihilation was remarkably suppressed due to the rapid dissociation of triplet pairs, leading to long-lived free triplets. In addition, the low light-harvesting ability of Pc in the visible region was promoted by the efficient energy transfer (99 ± 5.8%) from the QDs to Pc. The synergistically enhanced light-harvesting ability, high triplet yield, and long-lived triplet lifetime of the SF system on nanointerfaces could pave the way for an unmatched advantage of SF. acceptedVersion

Semiconductor quantum dot superlattices (QDSLs) have attracted much attention as key materials for realizing new optoelectronic devices such as solar cells with high conversion efficiency and thermoelectric elements with high electrical conductivity. To improve the charge transport properties of QDSL-based optoelectronic devices, it is important that the QD structures form minibands, which are the coupled electronic states between QDs. A shorter inter-QD distance and a periodic arrangement of QDs are the essential conditions for the formation of minibands. In this study, we use CdTe QDs capped with short ligands of N-acetyl-l cysteine (NAC) to fabricate three-dimensional QD assemblies by utilizing chemical bonding between NACs. Absorption spectra clearly display the quantum resonance phenomenon originating from the coupling of the wave functions between the adjacent QDs in CdTe QD assemblies. Furthermore, we demonstrate the formation of minibands in CdTe QD assemblies by examining both, the excitation energy dependence of photoluminescence (PL) spectra and the detection energy dependence of PL excitation spectra. The fabrication method of QD assemblies utilizing chemical bonding between NACs can be applied to all QDs capped with NAC as a ligand.

The orientation of a molecule on a metal surface can impact the performance of electronic devices fabricated from organic materials. This orientation effect of physiosorbed or weakly chemisorbed mo...

This paper reports on durable and nearly temperature-independent (at 298–328 K) T-type photochromism of colloidal Cu-doped ZnS nanocrystals (NCs). The color of Cu-doped ZnS NC powder changes from pale yellow to dark gray by UV light irradiation, and the color changes back to pale yellow on a time scale of several tens of seconds to minutes after stopping the light irradiation, while the decoloration reaction is accelerated to submillisecond in solutions. This decoloration reaction is much faster than those of conventional inorganic photochromic materials. The origin of the reversible photoinduced coloration is revealed to be a strong optical transition involving a delocalized surface hole which survives over a minute after escaping from intraparticle carrier recombination due to electron-hopping dissociation. ZnS NCs can be easily prepared in a water-mediated one-pot synthesis and are less toxic. Therefore, they are promising for large-scale photochromic applications such as windows and building materials in addition to conventional photochromic applications. Moreover, the present study demonstrates the importance of excited carrier dynamics and trap depths, resulting in coloration over minutes not only for photochromic nanomaterials but also for various advanced photofunctional materials, such as long persistent luminescent materials and photocatalytic nanomaterials.

Quantum dot superlattices (QDSLs), which are one-, two-, and three-dimensional periodic superlattices composed of QDs, induce dimensionality dependent quantum resonance among component QDs and thus represent a new type of condensed matter exhibiting novel energy, exciton, and carrier dynamics. We focused on the two important parameters, dimensionality and temperature, and identified their correlated roles to determine the electronic and photoexcited properties intrinsic to each QDSL at each dimensionality and temperature. We computationally demonstrated that the multiple exciton generation is significantly accelerated at higher temperature especially in the higher-dimensional QDSLs, indicating their great advantage especially at ambient temperature compared to an isolated zero-dimensional QD. Both dimensionality and temperature can be crucial and correlated parameters for independent tailoring of the properties of the QDSLs without changing the size, shape, and compositions of component QDs. The physical insights and advantage of the QDSLs we found here will lead to designing efficient and space-saving optoelectronic and photovoltaic devices that work at ambient temperature.

The formation of minibands in quantum dot (QD) superlattices (SLs) dramatically increases the mobility of carriers, giving a new way to apply QDs for optoelectronic devices. In previous studies on QDSLs, only a few studies have investigated the temperature dependence of the photoluminescence (PL) properties of QDSLs focusing on the formation of minibands. Here, ......

Differences in properties such as phase-transition temperature and transport coefficients among liquids of different isotopic compositions, hydrogen, deuterium, and tritium, should originate from their differently pronounced nuclear quantum effects (NQEs) rather than from any subtle difference in the electronic interaction potentials. Accurate and efficient determination of structural and dynamical isotopic effects in the quantum liquids still remains as one of the challenging problems in condensed-phase physics. With a recently developed nonempirical real-time molecular dynamics method which describes nonspherical molecules with the NQEs, we computationally realized and investigated dynamical and quantum isotopic effects of not only traditionally studied isotopes, hydrogen, and deuterium but also a lesser known radioisotope, tritium, in broad thermodynamic conditions from normal liquid to weakly and strongly cooled liquids, which have been hindered by rapid crystallization in spite of numerous experimental attempts at supercooling. Reproducing the previously reported experimental isotope dependence on the bond length and vibrational frequencies of hydrogen, deuterium, and tritium liquids, we further demonstrate that distinctive isotope effects appear in their intermolecular and intramolecular structure and dynamics not only at lower temperature but also at higher temperature, which none has so far been able to obtain quantitative results for realistic systems. Rationalization of their physical origins and the obtained physical insights will help future experimental searching and monitoring intermolecular and intramolecular dynamics and structures of these isotopes not only in normal liquid but also in supercooled liquid.

The prevalence of the condensed phase, interpenetration, and fragility of ruesoporous coordination polymers (meso-PCPs) featuring dense open metal sites (OMSs) place strict limitations en their preparation, as revealed by experimental and `theoretical reticular chemistry investigations. Herein, we propose a rational design of stabilized high-porosity meso-PCPs, employing a `low-symmetry ligand in combination with the shortest linker, formic acid. The resulting dimeric dusters (PCP-31 and PCP-32) exhibit high surface areas, ultrahigh porosities, and high OMS derisities (3.76 and 3.29 nmol g(-1) respectively), enabling highly selective- and effective separation of C2H2 from C2H2/CO2 mixtures at 298 K, as verified by binding energy (BE) and electrostatic potentials (ESP) calculations.

Proximate nitrogen-vacancy (NV) defects with interdefect interaction may establish a new kind of quantum qubit network to explore controlled multibody quantum dynamics. In particular, by introducing the critical distance and favorable orientation between a pair of NV defects, the quantum resonance (QR) can be induced. Here, we present the first real-time depolarization and phonon dynamics on the excited state at ambient temperature which are intrinsic to the proximate multi-NV defects. We computationally demonstrate that the QR can effectively change the major properties of the multi-NV defects, such as orbital degeneracy, orbital delocalization, local phonon modes, electron-phonon coupling, and orbital depolarization dynamics, elucidating the physical mechanisms and finding the key factors to control them. The physical insights provide a starting point for the positioning accuracy of NV defects and creation protocols with broad implications for magnetometry, quantum information, nanophotonics, sensing, and spectroscopy, allowing the QR to be a new means of physical manipulation.

CdTe and CdTe/CdS quantum dots (QDs) were synthesized via hydrothermal method in one-step processes just by controlling reaction time. A gradual thermal decomposition of thiol ligand N-acetyl-l-cysteine results in formation of a CdS shell on a CdTe core. The experimental results of X-ray diffraction and energy dispersive X-ray spectroscopy indicated that growth of the CdS shell started in a longer reaction time than 30 minutes and that the thickness of the CdS shell increased with increasing the reaction time. The CdTe/CdS QD exhibited a longer photoluminescence-decay time than the CdTe core QD due to the type-II band alignment, and the decay time in the CdTe/CdS QDs increased with an increase in the reaction time. The increase in the decay time in the CdTe/CdS QDs was qualitatively reproduced by a decrease in an overlap integral of electron and hole wave functions caused by an increase of the CdS shell thickness.

We have developed a quantum molecular dynamics simulation method which can widely search hydrogen systems from an isolated hydrogen molecule to condensed hydrogen liquid, solid and supercooled liquid of strong nuclear quantumness such as zero-point energy and nuclear delocalization. We will report our recent results on various condensed phases of hydrogen molecules including unexplored low-temperature supercooled phases, suggesting new insights and guiding data useful for future experiments.

High separation efficiency is very important for process of pressure swing adsorption (PSA) in the industry. Herein, we propose a fine design of chemically stable porous coordination polymers (PCPs) with optimized nanochannel by strategy of inserting and shifting shortest alkyl group on T-shaped ligand. Remarkably, the synergistic effect of optimized nanochannel, unique crystal morphology and fitted channel enable sharply enhanced breakthrough efficiency of C2H6/4/CH4, 1.17 or 0.77 g of CH4 can be separated from corresponding dual mixtures (2/8, v/v) by 1 g of NTU-25 at 273 K, which was further validated and understood by controlled experiments and density functional theory (DFT) computations.

Supercooled hydrogen liquid as well as superfluid have continued to elude experimental observation due to rapid crystallization. We computationally realized and investigated supercooled hydrogen liquid by a recently developed non-empirical real-time molecular dynamics method, which describes non-spherical hydrogen molecules with the nuclear quantum effects. We demonstrated that the hydrogen supercooled liquid is not a simply cooled liquid but rather exhibits intrinsic structural and dynamical characters including a precursor of tunneling and superfluidity which neither normal hydrogen liquid nor solid possesses. All of the insights provide a milestone for planning experiments of metastable hydrogen systems like glassy and superfluid states and for identifying various unknown hydrogen phases.

Quantum confinement in nanoscale materials allows Auger-type electron-hole energy exchange. We show by direct time-domain atomistic simulation and analytic theory that Auger processes give rise to a new mechanism of charge transfer (CT) on the nanoscale. Auger-assisted CT eliminates the renown Marcus inverted regime, rationalizing recent experiments on CT from quantum dots to molecular adsorbates. The ab initio simulation reveals a complex interplay of the electron-hole and charge-phonon channels of energy exchange, demonstrating a variety of CT scenarios. The developed Marcus rate theory for Auger-assisted CT describes, without adjustable parameters, the experimental plateau of the CT rate in the region of large donor-acceptor energy gap. The analytic theory and atomistic insights apply broadly to charge and energy transfer in nanoscale systems.

The possibility of precisely manipulating interior nanospace, which can be adjusted by ligand-attaching down to the subnanometer regime, in a hyperstructured quantum dot (QD) superlattice (QDSL) induces a new kind of collective resonant coupling among QDs and opens up new opportunities for developing advanced optoelectric and photovoltaic devices. Here, we report the first real-time dynamics simulations of the multiple exciton generation (MEG) in one-, two-, and three-dimensional (1D, 2D, and 3D) hyperstructured H-passivated Si QDSLs, accounting for thermally fluctuating band energies and phonon dynamics obtained by finite-temperature ab initio molecular dynamics simulations. We computationally demonstrated that the MEG was significantly accelerated, especially in the 3D QDSL compared to the 1D and 2D QDSLs. The MEG acceleration in the 3D QDSL was almost 1.9 times the isolated QD case. The dimension-dependent MEG acceleration was attributed not only to the static density of states but also to the dynamical electron-phonon couplings depending on the dimensionality of the hyperstructured QDSL, which is effectively controlled by the interior nanospace. Such dimension-dependent modifications originated from the short-range quantum resonance among component QDs and were intrinsic to the hyperstructured QDSL. We propose that photoexcited dynamics including the MEG process can be effectively controlled by only manipulating the interior nanospace of the hyperstructured QDSL without changing component QD size, shape, compositions, ligand, etc.

Achieving a direct nonequilibrium simulation for hydrogen systems has been quite challenging because nuclear quantum effects (NQEs) have to be taken into account. We directly simulated nonequilibrium hydrogen molecules under a temperature gradient with the recently developed nonempirical molecular dynamics method, which describes nonspherical hydrogen molecules with the NQEs. We found dynamical ordering purely induced by heat flux, which should be distinguished from static ordering like orientational alignment, as decelerated translational motions and enhanced intensity of H–H vibrational power spectra despite the little structural ordering. This dynamical ordering, which was enhanced with stronger heat flux while independent of system size, can be regarded as self-solidification of hydrogen molecules for their efficient heat conduction.

To understand anomalous energetics and dynamics in water, nuclear quantum effects such as zero-point energy and delocalization of wave packets (WPs) representing water hydrogen atoms should be essential. However, since quantum calculations of many-body dynamics are highly complicated in general, none has yet directly viewed the quantum WP dynamics of hydrogen atoms in liquid water. Our semiquantum molecular dynamics simulation for the first time made it possible to observe the hydrogen WP dynamics in liquid water. Here, we demonstrate that the microscopic WP dynamics are closely correlated to and play key roles in the dynamical rearrangements in the hydrogen-bond network (HBN) of liquid water. Especially, the memory loss of the dipolar angle formed by two waters is accelerated with the nuclear quantum effect introduced by the nuclear WP, rationalizing the faster memory decay of the HBN in the quantum liquid water. We found the quantum effects of hydrogen atoms on mesoscopic liquid water behaviors such as intermittent collective motions associated with the rearrangement of HBN and the concomitant fluctuation and relaxation. Our results will provide new physical insights on HBN dynamics in water whose significance is not limited to the pure liquid dynamics but also for understanding chemical and biological reactions in liquid water.

The review discusses the results of ab initio time-dependent density functional theory and non-adiabatic molecular dynamics simulations of photoinduced dynamics of charges, excitons, plasmons, and phonons in semiconductor and metallic quantum dots (QDs). The simulations create an explicit time-domain representation of the excited-state processes, including elastic and inelastic electron–phonon scattering, multiple exciton generation, fission, and recombination. These nonequilibrium phenomena control the optical and electronic properties of QDs. Our approach can account for QD size and shape, as well as chemical details of QD structure, such as dopants, defects, core/shell regions, surface ligands, and unsaturated bonds. Each of these variations significantly alters the properties of photoexcited QDs. The insights reported in this review provide a comprehensive understanding of the excited-state dynamics in QDs and suggest new ways of controlling the photo-induced processes. The design principles that follow, guide development of photovoltaic cells, electronic and spintronic devices, biological labels, and other systems rooted in the unique physical and chemical properties of nanoscale materials.

Although quantum confined nanomaterials, such as quantum dots (QDs) have emerged as a new class of light harvesting and charge separation materials for solar energy conversion, theoretical models for describing photoinduced charge transfer from these materials remain unclear. In this paper, we show that the rate of photoinduced electron transfer from QDs (CdS, CdSe, and CdTe) to molecular acceptors (anthraquinone, methylviologen, and methylene blue) increases at decreasing QD size (and increasing driving force), showing a lack of Marcus inverted regime behavior over an apparent driving force range of ∼0-1.3 V. We account for this unusual driving force dependence by proposing an Auger-assisted electron transfer model in which the transfer of the electron can be coupled to the excitation of the hole, circumventing the unfavorable Franck-Condon overlap in the Marcus inverted regime. This model is supported by computational studies of electron transfer and trapping processes in model QD-acceptor complexes.

Third-generation photovolatics require demanding cost and power conversion efficiency standards, which may be achieved through efficient exciton multiplication. Therefore, generating more than one electron-hole pair from the absorption of a single photon has vast ramifications on solar power conversion technology. Unlike their bulk counterparts, irradiated semiconductor quantum dots exhibit efficient exciton multiplication, due to confinement-enhanced Coulomb interactions and slower nonradiative losses. The exact characterization of the complicated photoexcited processes within quantum-dot photovoltaics is a work in progress. In this Account, we focus on the photophysics of nanocrystals and investigate three constituent processes of exciton multiplication, including photoexcitation, phonon-induced dephasing, and impact ionization. We quantify the role of each process in exciton multiplication through ab initio computation and analysis of many-electron wave functions. The probability of observing a multiple exciton in a photoexcited state is proportional to the magnitude of electron correlation, where correlated electrons can be simultaneously promoted across the band gap. Energies of multiple excitons are determined directly from the excited state wave functions, defining the threshold for multiple exciton generation. This threshold is strongly perturbed in the presence of surface defects, dopants, and ionization. Within a few femtoseconds following photoexcitation, the quantum state loses coherence through interactions with the vibrating atomic lattice. The phase relationship between single excitons and multiple excitons dissipates first, followed by multiple exciton fission. Single excitons are coupled to multiple excitons through Coulomb and electron-phonon interactions, and as a consequence, single excitons convert to multiple excitons and vice versa. Here, exciton multiplication depends on the initial energy and coupling magnitude and competes with electron-phonon energy relaxation. Multiple excitons are generated through impact ionization within picoseconds. The basis of exciton multiplication in quantum dots is the collective result of photoexcitation, dephasing, and nonadiabatic evolution. Each process is characterized by a distinct time-scale, and the overall multiple exciton generation dynamics is complete by about 10 ps. Without relying on semiempirical parameters, we computed quantum mechanical probabilities of multiple excitons for small model systems. Because exciton correlations and coherences are microscopic, quantum properties, results for small model systems can be extrapolated to larger, realistic quantum dots.

A semiquantal (SQ) molecular dynamics (MD) simulation method using spherical Gaussian wave packets (WPs) is applied to a microscopic analysis of hydrogen-bond (H-bond) exchange dynamics in liquid water. We focus on the molecular jump mechanism of H-bond reorientation dynamics proposed from a classical MD simulation by Laage and Hynes (Science 2006, 311, 832). As a notable quantum effect, broadenings of both the oxygen and hydrogen WPs of jumping water are observed associated with the H-bond switching events. Nonetheless, quantum effects on averaged trajectories of structural parameters measured with respect to the WP centers are rather minor. A 1/f fluctuation of local H-bond number is observed in both SQ and classical simulations. This is obtained straightforwardly from the real-time trajectories, in contrast with the originally found 1/f fluctuation (Sasai et al., J. Chem. Phys. 1992, 96, 3045) of the total potential energies collected at quenched inherent structures. The quantum effects are found to accelerate the relaxation of H-bond number fluctuation, which is reflected in the region near the lower bound of the 1/f behavior in the power spectra. New developments in the implementation of SQMD simulations including all atoms are also described. © 2012 Wiley Periodicals, Inc.

Quantum dot (QD) superlattices, periodically ordered array structures of QDs, are expected to provide novel photo-optical functions due to their resonant couplings between adjacent QDs. Here, we computationally demonstrated that electronic structures and phonon dynamics of a QD superlattice can be effectively and selectively controlled by manipulating its interior nanospace, where quantum resonance between neighboring QDs appears, rather than by changing component QD size, shape, compositions, etc. A simple H-passivated Si QD was examined to constitute one-, two-, and three-dimensional QD superlattices, and thermally fluctuating band energies and phonon modes were simulated by finite-temperature ab initio molecular dynamics (MD) simulations. The QD superlattice exhibited a decrease in the band gap energy enhanced by thermal modulations and also exhibited selective extraction of charge carriers out of the component QD, indicating its advantage as a promising platform for implementation in solar cells. Our dynamical phonon analyses based on the ab initio MD simulations revealed that THz-frequency phonon modes were created by an inter-QD crystalline lattice formed in the QD superlattice, which can contribute to low energy thermoelectric conversion and will be useful for direct observation of the dimension-dependent superlattice. Further, we found that crystalline and ligand-originated phonon modes inside each component QD can be independently controlled by asymmetry of the superlattice and by restriction of the interior nanospace, respectively. Taking into account the thermal effects at the finite temperature, we proposed guiding principles for designing efficient and space-saving QD superlattices to develop functional photovoltaic and thermoelectric devices.