Molecular Dipole Research Articles

Molecular structure and spectra of ytterbium dihalides from first principles

The molecular structure, vibrational frequencies, infrared intensities and electric dipole moments of ytterbium dihalides YbX2 (X = F, Cl, Br, I) in their ground electronic state are studied at the coupled-cluster singles, doubles and perturbative triples CCSD(T) level using a series of large all-electron basis sets together with the complete basis set (CBS) extrapolation procedure, and with both scalar-relativistic and spin–orbit coupling effects taken into account. Excitation energies of low-lying electronic states are calculated at the multireference configuration interaction, equation-of-motion CCSD and single-reference CCSD(T) levels of theory. For all of the molecules under study, the CCSD(T)/CBS equilibrium geometries are found to be non-linear (C2v symmetry). There is a rapid decrease in heights of the barriers to linearity on passing through the YbX2 molecular series from fluoride to iodide: 1587 → 261 → 110 → 7 (all in cm−1) for YbF2 → YbCl2 → YbBr2 → YbI2, respectively. The uncertainties in the molecular structure data published to date are discussed and resolved in the light of the present results.

Molecular dynamics characterization of the interfacial structure and forces of the methane-ethane sII gas hydrate interface

The nucleation of gas hydrates is of great interest in flow assurance, global energy demand, and carbon capture and storage. A complex molecular understanding is critical to control hydrate nucleation and growth in potential applications. Molecular dynamics is employed combined with the mechanical definition of surface tension to assess the surface stresses controlling interfacial behavior. We characterize the interfacial tension for sII methane/ethane hydrate and gas mixtures for different temperatures and pressures. We find that the surface tension trends positively with temperature in a balance of water-solid and water-gas interactions. The molecular dipole shows the complexities of water molecule behavior in small, compressed pre-melting layer that emerges as a quasi-liquid. These behaviors contribute to the developing knowledge base surrounding practical applications of this interface.

Enhancing the Performance of MoS2 Field-Effect Transistors Using Self-Assembled Monolayers: A Promising Strategy to Alleviate Dielectric Layer Scattering and Improve Device Performance.

Field-effect transistors (FETs) based on two-dimensional molybdenum disulfide (2D-MoS2) have great potential in electronic and optoelectronic applications, but the performances of these devices still face challenges such as scattering at the contact interface, which results in reduced mobility. In this work, we fabricated high-performance MoS2-FETs by inserting self-assembling monolayers (SAMs) between MoS2 and a SiO2 dielectric layer. The interface properties of MoS2/SiO2 were studied after the inductions of three different SAM structures including (perfluorophenyl)methyl phosphonic acid (PFPA), (4-aminobutyl) phosphonic acid (ABPA), and octadecylphosphonic acid (ODPA). The SiO2/ABPA/MoS2-FET exhibited significantly improved performances with the highest mobility of 528.7 cm2 V-1 s-1, which is 7.5 times that of SiO2/MoS2-FET, and an on/off ratio of ~106. Additionally, we investigated the effects of SAM molecular dipole vectors on device performances using density functional theory (DFT). Moreover, the first-principle calculations showed that ABPA SAMs reduced the frequencies of acoustic and optical phonons in the SiO2 dielectric layer, thereby suppressing the phonon scattering to the MoS2 channel and further improving the device's performance. This work provided a strategy for high-performance MoS2-FET fabrication by improving interface properties.

Asymmetric Charge Distribution in One-dimensional Metal-Organic Assemblies to Promote Photocatalytic Hydrogen Evolution.

The local charge distribution of photocatalyst is crucial to the catalytic activity due to its influence on the charge separation process. Herein, we report two one-dimensional Ni-based metal-organic assemblies for efficient photocatalytic hydrogen evolution without using noble-metal cocatalysts. By adjusting the aromatic ring in the center of the tricarboxylic ligand, the photocatalytic hydrogen evolution activity was increased from 1715 to 2652 μmol h-1 g-1. The detailed mechanism study shows that the introduced nitrogen atoms in the ligands of the metal-organic coordination assembly could modulate the local charge distribution, and yielding a significant enhancement of the molecular dipole moment which engenders a propulsive force for the effective separation and transport of photoinduced charge carriers. This work provides insights into the local charge distribution via ligand modulation for enhancing the activity of photocatalysts.

Molecular interactions of the antioxidant in the coolant oil for energy transformers: Dielectric and simulation studies

This research paper presents experimental and theoretical findings concerning the blending of mineral oil and vegetable oils, both with and without antioxidants. The study analyses a variety of parameters for different blends of mineral and vegetable oils, including breakdown voltage, ageing resistance, dielectric constant, viscosity, dissipation factor, surface tension, flash point, and fire point. The study was further extended to investigate the effects of varying the amount of antioxidants added to mineral oil blends with different vegetable oils. The best transformer insulating solution is found by extensive analyses that include measurements of breakdown voltage, flash point, fire point, and surface tension. This blends’ properties with antioxidant are either better than pure mineral oil or comparable to mineral oil. Density functional theory (DFT) analyses the molecular structure and dipole moment of an antioxidant. Molecular dynamics simulation method (MD) analysis of the average water residual time – periods of an antioxidant will show the stability of H-bond interactions. The primary objective of this experiment is to unveil a novel liquid-insulating material that not only excels in dielectric performance but also aligns with environmentally friendly practices.

Engineering an A-D-A structure to enhance internal electric fields in silica-PDI-decorated vertical graphene for efficient photocatalytic oxidation

Efficient charge separation and transfer are crucial for elevating photocatalytic oxidation, and designing a photocatalyst structure with strong internal electric fields (IEF) hold promise for addressing the issue. Herein, we synthesized a silica-PDI (silica-perylene diimides) decorated vertical graphene (s-PDI@VG) architecture with an Acceptor-Donor-Acceptor (A-D-A) structure. The A-D-A configuration facilitated electron transfer from tertiary N-atom to perylene tetracarboxylic dianhydride (PTCDA) and flower-like vertical graphene (VG), resulting in a larger molecular dipole moment of s-PDI@VG compared to PTCDA and s-PDI. Consequently, an IEF with 7.5 times higher than PTCDA and 4.8 times higher than s-PDI was built, which is beneficial for photogenerated charge separation. Additionally, the valence band (VB) of s-PDI@VG deepened from 1.43 eV to 1.62 eV, enabling it to afford a strong oxidation potential. As a proof-of-concept, the 3D s-PDI@VG photocatalyst demonstrated favorable persulfate (PMS) activation and pollutant adsorption, resulting in 1.6 times higher photogenerated holes based on LSCM results. This photocatalyst also achieved 98.2 % mineralization of high-ionization-potential (h-IP) organics within 30 min. This work offers insights into a novel photocatalytic oxidation strategy with high mineralization by engineering A-D-A structure and enhancing the IEF strength of photocatalyst molecules.

Synergistic Molecular Alignment and Dipole Polarization in Stretched Nafion/Poly(vinylidene fluoride) Blend Membranes for High Proton Conduction in PEMFCs.

The nanostructure of Nafion and poly(vinylidene fluoride) (PVDF) blend membranes is successfully aligned through a mechanical uniaxial stretching method. The phase-separated morphology of Nafion molecules distinctly forms hydrophilic proton channels with increased connectivity, resulting in enhanced proton conductivity. Additionally, the crystalline phase of PVDF molecules undergoes a successful transformation from the α- to β-phase during membrane stretching, demonstrating an alignment of fluorine and hydrogen atoms with a TTTT(trans) structure. The aligned nanostructure of the blend film, combined with the dipole polarization of the β-phase PVDF, synergistically enhances the proton conduction through the membrane for operating proton-exchange membrane fuel cells (PEMFCs). The controlled structures of the blend membranes are thoroughly investigated using atomic force microscopy and small-angle X-ray scattering. Furthermore, the improved in-plane proton conductivity facilitates increased proton conduction at the interface between the membrane and catalyst layer in the membrane-electrode assembly, ultimately enhancing the power generation of PEMFCs.

Competitive Adsorptive Mechanism of H2/N2 in LTA/FAU Zeolites by Molecular Simulations and Experiments.

For industrial tail gas to be converted into high-purity hydrogen, the H2-N2 mixture needs to be separated efficiently. This work examined the adsorption characteristics and competitive mechanisms of H2 and N2 on LTA- and FAU-type zeolites, at 77 K, 298 K, and 0.1-10 bar by thoroughly analyzing results of adsorption capacity experiments and molecular simulations. In the Grand Canonical Monte Carlo (GCMC) simulations, the force field causing a molecular dipole of H2 and the polarization force field of N2 are first applied. The accuracy of the force field was experimentally verified. The findings indicate that N2 and H2 loading on Ca-FAU (Ca-LTA) are higher than Na-FAU (Na-LTA). On NaX at 77 K, the highest adsorption selectivity (N2/H2) is observed; on NaA at 298 K, it is the opposite. The GCMC data findings demonstrate that H2 and N2 have remarkably similar adsorption sites, with framework oxygen atoms and non-framework cations serving as the main adsorption sites for adsorbate molecules. Furthermore, the rate at which H2 diffuses is higher than that of N2. The study of redistribution charge before and after adsorption demonstrated that N2 has a greater affinity for the framework oxygen atoms than H2. This study provides a molecular theoretical foundation for the adsorption behavior of H2-N2 mixture in zeolites.

Highly thermo- and photo-stable acceptor-acceptor′-acceptor type perylenediimide dimeric acceptors: Role of monofluorinating the central benzo[c][1,2,5]thiadiazole linking core

Acceptor-Acceptor′-Acceptor (A-A′-A) type perylene diimide (PDI)-based dimeric non-fullerene electron acceptors (NFEAs) have drawn the special attention but have not been sufficiently exploited. With that in mind, two A-A′-A type NFEAs, DTBT-(PDI-HD)2 and DTFBT-(PDI-HD)2, in which 4,7-di(thien-2-yl)benzo[c][1,2,5]thiadiazole (DTBT) and its monofluorinated 4,7-di(thien-2-yl)-5-fluorobenzo[c][1,2,5]thiadiazole (DTFBT) as central linkers, both N,N′-(2-hexyldecyl)-PDI (PDI-HD) units as flanked biwings, were successfully synthesized to probe into the influence of different electron-deficient linkers on thermo- and photo-stability, absorption, energy level, molecular configuration, exciton dissociation, charge mobility and solar cell performance. Both A-A′-A type acceptors with excellent thermal- and photo-stability possessed the complementary absorption ranging from 300 nm to 780 nm and matched ELUMO of −3.84 eV to −3.91 eV when pairing with PTB7-Th. Moreover, increased molecular dipole moment, slightly blue-shifted the maximum absorption peak, decreased the absorption coefficient and deepened the ELUMO were found after monofluorinating the benzothiadiazole. Conversely, the augmented aggregation both in solution and film effectively tuned the miscibility and morphology of active layer, contributing to the improvements of the exciton dissociation, charge mobility and photocurrent. Benefiting from this, monofluorinating the electron-deficient benzothiadiazole linker made the JSC increase from 3.72 to 7.19 mA cm−2, the FF enhance from 34.99 % to 38.18 % in DTFBT-(PDI-HD)2-based device when blending with PTB7-Th, contributing to 1.09 times increased PCE from 1.03 % to 2.15 % even in the adverse condition of 0.01 V dropped VOC. These results suggest that monofluorinating the electron-deficient benzothiadiazole linker is an effective approach for boosting the device efficiency via tuning the molecular aggregation and affecting the related morphology and charge mobility during the A-A′-A type PDI-based NFEAs.

Novel furan-containing linear polymer with strong built-in electric field for H2O2 photosynthesis

Using oxygen and water as raw materials, the photocatalytic production of H2O2 is a promising pathway. However, the limited charge separation efficiency represents a significant challenge in the photocatalysis field, as it impedes the generation of H2O2. Herein, a novel highly crystalline linear polymer has been synthesized here by bridging the strongly electronegative furan group with a diphenyl group, in order to adjust its molecular dipole moment to construct an intrinsic electric field to optimize photocatalytic performance. The optimal sample exhibited the best H2O2 synthesis rate of 2686 μmol·g−1·h−1 under pure water conditions, which is the best-performing linear conjugated polymer reported to date for H2O2 photosynthesis system. Importantly, the large internal dipole moment within furan-diphenyl linear polymer, together with the ordered crystalline structure induced robust built-in electric field, can facilitate migration and separation of photogenerated charge carriers. Manipulating molecular dipoles to enhance the built-in electric field can significantly improve photocatalytic activity, providing a new perspective for the rational design of functional linear conjugated polymers in green chemistry and sustainable production.

How Molecular Orientation Affects the Static Permittivity Profile of the Polar and Nonpolar Liquid-Liquid Interface.

The dielectric permittivity across the liquid-liquid interface presents an intrinsic response, with respect to the instantaneous interface reference. We hypothesize that dielectric responses across the nonpolar and polar liquid-liquid interfaces have different behaviors and underlying mechanisms. Molecular dynamics simulations were used to compare and contrast the dielectric response of a nonpolar (1,2-dichloroethane/water) and a polar (1-octanol/water) liquid-liquid interface system. We found that the enhanced dielectric permittivity at the nonpolar interface is attributed to the increased water dipole orientation and polarization density. In the case of the polar interface, strong association of the immiscible solvents inhibits the molecular dipole orientation, counteracting the effect from the enhanced surface water polarization density and resulting in a standard dielectric response. Detailed knowledge of the hydrogen bond networks and molecular dipole orientation with respect to the specific instantaneous interfacial and bulk regions reveals the effect of molecular proximity and the interaction with the opposing interfacial molecules on the mechanism of the dielectric permittivity response across the liquid-liquid interface phase boundary.

Dimensional dependence of a molecular-polariton mode number

Vibrational and electronic strong coupling of light with molecular excitations has shown promise for modifying chemical reaction rates. However, the Tavis–Cummings model often used to model such polaritonic chemistry considers only a single discrete cavity mode coupled with the molecular modes, while experimental systems generally consist of a larger number of molecules in cavities with a continuum of modes. Here, we model the polaritonic effects of multimode cavities of arbitrary dimensions and filled with a large number of molecules. We obtain the dependence of the effects on the dimensionality of the cavity, the molecular oscillator strength, and molecular concentration. Combining our model with the transition state theory, we show that polaritonic effects can be altered by a few orders of magnitude compared to including only a single cavity mode, and that the effect is stronger with a larger molecular dipole moment and molecular concentration. However, the change remains negligibly small for realistic chemical systems due to the large number of dark states.

Quantifying Induced Dipole Effects in Small Molecule Permeation in a Model Phospholipid Bilayer.

The cell membrane functions as a semipermeable barrier that governs the transport of materials into and out of cells. The bilayer features a distinct dielectric gradient due to the amphiphilic nature of its lipid components. This gradient influences various aspects of small molecule permeation and the folding and functioning of membrane proteins. Here, we employ polarizable molecular dynamics simulations to elucidate the impact of the electronic environment on the permeation process. We simulated eight distinct amino-acid side chain analogs within a 1-palmitoyl-2-oleoyl-sn-glycero-3-phosphocholine bilayer using the Drude polarizable force field (FF). Our approach includes both unbiased and umbrella sampling simulations. By using a polarizable FF, we sought to investigate explicit dipole responses in relation to local electric fields along the membrane normal. We evaluate molecular dipole moments, which exhibit variation based on their localization within the membrane, and compare the outcomes with analogous simulations using the nonpolarizable CHARMM36 FF. This comparative analysis aims to discern characteristic differences in the free energy surfaces of permeation for the various amino-acid analogs. Our results provide the first systematic quantification of the impact of employing an explicitly polarizable FF in this context compared to the fixed-charge convention inherent to nonpolarizable FFs, which may not fully capture the influence of the membrane dielectric gradient.

Lattice Dynamics of Quasi-2D Perovskites from First Principles.

We present the vibrational properties and phonon dispersion for quasi-2D hybrid organic-inorganic perovskites (BA)2CsPb2I7, (HA)2CsPb2I7, (BA)2(MA)Pb2I7, and (HA)2(MA)Pb2I7 calculated from first principles. Given the highly complex nature of these compounds, we first perform careful benchmarking and convergence testing to identify suitable parameters to describe their structural features and vibrational properties. We find that the inclusion of van der Waals corrections on top of generalized gradient approximation (GGA) exchange-correlation functionals provides the best agreement for the equilibrium structure relative to experimental data. We also investigate the impact of the molecular orientation on the equilibrium structure of these layered perovskite systems. Our results suggest ground state ferroelectric alignment of molecular dipoles in the out-of-plane direction is unlikely and support the assignment of the centrosymmetric space group for the low-temperature phase of (HA)2(MA)Pb2I7. Finally, we compute vibrational properties under the harmonic approximation. We find that stringent energy cut-offs are required to obtain well-converged phonon properties, and once converged, the harmonic approximation can capture key physics for such a large, hybrid inorganic-organic system with vastly different atom types, masses, and interatomic interactions. We discuss the obtained phonon modes and dispersion behavior in the context of known properties for bulk 3D perovskites and ligand molecular crystals. While many vibrational properties are inherited from the parent systems, we also observe unique coupled vibrations that cannot be associated with vibrations of the pure constituent perovskite and ligand subphases. Energy dispersion of the low energy phonon branches primarily occurs in the in-plane direction and within the perovskite subphase and arises from bending and breathing modes of the equatorial Pb-I network within the perovskite octahedral plane. The analysis herein provides the foundation for future investigations on this class of materials, such as exciton-phonon coupling, phase transitions, and general temperature-dependent properties.

Decoding the Impact of Molecular Configuration on High‐Efficiency Blue Hot Exciton Emitters

AbstractRealizing highly efficient organic light‐emitting diodes (OLEDs) based on “hot exciton” emitters is crucial for the widespread use of purely organic electroluminescence. Herein, it is demonstrated that the radiative decay rate, modulated by molecular configuration, plays a vital role in determining the optoelectronic properties of hot exciton materials. The proof‐of‐concept isomers, TPA‐1IPCN and TPA‐3IPCN, and TPA‐1IANCN and TPA‐3IANCN are intentionally designed and successfully synthesized. By employing a novel donor–acceptor–acceptor (D–A'–A) molecular architecture, implementing a molecular isomerization strategy, incorporating diverse steric hindrance moieties, and strategically manipulating the positioning of functional groups, precise modulation of the molecular configuration can be achieved to enable accurate regulation of the radiative decay rate. Consequently, various optoelectronic properties, including photoluminescent wavelength, photoluminescence quantum yield, fluorescence lifetime, packing mode in aggregated state, and molecular horizontal dipole ratios in films, undergo significant modifications. As a result, non‐doped blue OLED based on TPA‐1IPCN exhibits outstanding maximum external quantum efficiency (EQE) of 10.3% with minimal efficiency roll‐off—one of the highest reported values for blue OLEDs based on hot exciton materials.

Quamtum Mechanical Study on Structural and Electronic Properties of Tert-Butyl Based Bridged Dithiophene Oxide Derivatives

Computational modeling is vital to designing and creating organic semiconductors used in solar cells, organic field-effect transistors, and other areas. This work studied the structural and electronic features of a group of substituted tert-butyl bridged dithiophene oxide derivatives using Density Functional Theory (DFT) calculations. Geometry improvements were carried out using the B3LYP hybrid functional and the 6-31G(d,p) basis set in Gaussian 09. Molecular shapes, bond lengths, bond angles, and dihedral angles were studied to find out how substitution patterns change the packing and conformation of molecules. Energy levels, distribution, and makeup of frontier molecular orbitals were found. This calculation also included finding other electronic qualities, such as electronic charges, dipole moments, and polarizabilities. Findings show that tert-butyl substitution makes the molecular backbone stiffer and limits its ability to twist compared to similar molecules that have not been replaced. The chemical geometry stays mostly the same when electron-withdrawing or electron-donating substituents are added to the tert- butyl groups. Nevertheless, the strength and location of substituents have a significant impact on frontier orbital energies. The HOMO-LUMO gap grew significantly when the nitro or cyano groups firmly pulled electrons away from derivatives. For successful charge transport, electron density plots show that the HOMO and LUMO are mainly located on the thiophene and substituent moieties, respectively. Molecular dipole moments are also strongly affected by the electronic features of substituents. This research shows how to change the optoelectronic properties of tert-butyl-based dithiophene oxide derivatives and how their structure-property relationships can be improved. The results help makes new organic semiconductors that work better in various electronic and optoelectronic uses.

Ultrafast Picometer-Resolved Molecular Structure Imaging by Laser-Induced High-Order Harmonics.

Real-time visualization of molecular transformations is a captivating yet challenging frontier of ultrafast optical science and physical chemistry. While ultrafast x-ray and electron diffraction methods can achieve the needed subangstrom spatial resolution, their temporal resolution is still limited to hundreds of femtoseconds, much longer than the few femtoseconds required to probe real-time molecular dynamics. Here, we show that high-order harmonics generated by intense femtosecond lasers can be used to image molecules with few-ten-attosecond temporal resolution and few-picometer spatial resolution. This is achieved by exploiting the sensitive dependence of molecular recombination dipole moment to the geometry of the molecule at the time of harmonic emission. In a proof-of-principle experiment, we have applied this high-harmonic structure imaging (HHSI) method to monitor the structural rearrangement in NH_{3}, ND_{3}, and N_{2} from one to a few femtoseconds after the molecule is ionized by an intense laser. Our findings establish HHSI as an effective approach to resolve molecular dynamics with unprecedented spatiotemporal resolution, which can be extended to trace photochemical reactions in the future.

Enhancing the dielectric constant of zwitterionic liquids via dipole moment and anion chemistry

The dielectric constant is a critical parameter in many energy-related applications. Typically, increasing the dielectric constant of soft materials involves adding high dielectric constant polar liquids or inorganic fillers, but there are limitations to this approach due to safety concerns with volatile and flammable solvents and the agglomeration of inorganic fillers. An alternative approach is to add zwitterionic liquids that exhibit exceptionally high dielectric constants with negligible volatility. Here, we report the synthesis of a series of zwitterionic liquids containing an imidazolium cation, exhibiting the highest dielectric constant among all organic molecules (∼350 at 293 K). The cation–anion linkage was tailored in a wide range between three and nine carbons, rendering the zwitterion dipole from 25 to 52 D. Comparing the dielectric constant for zwitterions with different anions (i.e., sulfonylimide, sulfonate, and carboxylate) reveals the beneficial impacts of the delocalized sulfonylimide anion vs the carboxylate anion due to the enlarged molecular dipole and more homogenous liquid morphology. Molecular dipole and liquid morphology are identified as the keys to developing high dielectric constant zwitterionic liquids. The extremely high dielectric constant accessible with the proposed molecular design paves new avenues for developing high dielectric constant zwitterions that act as dielectricizers.

Nontrivial effects of geometric and charge defects on one-dimensional confined water

Water confined within nanochannels with specific functionalities serves as the foundation for a variety of emerging nanofluidic applications. However, the structure and dynamics of the confined liquid are susceptibly influenced by practically hard-to-avoid defects, yet knowledge of this fact remains largely unexplored. Here, using extensive molecular dynamics simulations, we elucidate the significant influence of geometric and charge defects on one-dimensional confined water. We show that the two types of defects can both reshape the water density distribution by constraining the translocation of water molecules along the circumferential direction. In addition to structural alterations, collective translocation and rotation of water slabs arise during transportation under external pressure. Below the temperature threshold marking the initiation of liquid-solid transition, the geometric defect retards water diffusion through a pinning effect, while the charge defect induces an anti-freezing effect. The latter is attributed to the electrostatic interaction between the charge defect and water molecules that hinders the formation of a stable hydrogen bond network by disrupting molecular dipole orientation. Consequently, this behavior results in a reduction in the number and lifetime of hydrogen bonds within the phase transition interval. The distinct roles of the two types of defects could be utilized to control the structure and dynamics of confined liquids that may result in distinct functionalities for nanofluidic applications.

Hierarchical self-constructed molecular layers of small bifunctional molecules with strong molecular dipole moments for improvement of quantum efficiency in inorganic quantum dots

Hierarchically structured self-assembled molecular layers are functionally versatile and structurally tunable, which are nanoscale molecular building blocks with a wide range of applications from biosensing systems to optoelectronic devices. Herein, we present a facile and effective strategy to fabricate hierarchical self-constructed molecular layers comprising small bifunctional molecules with strong molecular dipole moments for improvement of quantum efficiency in inorganic quantum dots (QDs) by using the cooperative interfacial self-assembly of hydrophilic bifunctional molecules on the polar electrode surface. The spontaneous construction of nanostructured molecular layers with different molecular dipole moments was simply achieved through solution-dipping and in situ interfacial self-organization of 3-mercaptopropionic acid or 1-propanethiol molecules on the surface of indium tin oxide (ITO) anode. It is experimentally revealed that these functional molecules formed uniform and ultrathin self-constructed molecular nanolayers on the ITO surface via covalent bonding, where bifunctional 3-mercaptopropionic acid molecules induced a polar molecular surface of thiol groups with strong dipole moments, whereas 1-propanethiol molecules formed a relatively hydrophobic surface of short alkyl chains with weak dipole moments. In addition, the nanoscale ultrathin nature of these molecular layers afforded high visible light transmittance comparable to that of pristine ITO substrate. The electro-optical properties of the QD cells revealed that hierarchical self-constructed molecular nanolayer with strong molecular dipole moments exhibited superior current and luminescent properties with a 162% improvement in external quantum efficiency relative to those of a conventional QD device without molecular layer. Furthermore, the self-assembled molecular nanolayer of 3-mercaptopropionic acid exhibited a higher luminescent efficiency than 1-propanethiol-based nanolayer owing to the increased hole mobility of thiol-based molecular layer with strong dipole moments.